Ucalgary - 2015 - Araneda Arango - Juan

University of Calgary
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Graduate Studies The Vault: Electronic Theses and Dissertations
2015-04-20
Synthesis, Characterization and Reactivity of

Pi-Conjugated Organoboron Compounds
Araneda Arango, Juan
Araneda Arango, J. (2015). Synthesis, Characterization and Reactivity of Pi-Conjugated

Organoboron Compounds (Unpublished doctoral thesis). University of Calgary, Calgary, AB.
doi:10.11575/PRISM/27955
http://hdl.handle.net/11023/2142
doctoral thesis
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UNIVERSITY OF CALGARY
Synthesis, Characterization and Reactivity of Pi-Conjugated Organoboron Compounds
by
Juan Felipe Araneda Arango
A THESIS
SUBMITTED TO THE FACULTY OF GRADUATE STUDIES
IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE
DEGREE OF DOCTOR OF PHILOSOPHY
GRADUATE PROGRAM IN CHEMISTRY
CALGARY, ALBERTA
April, 2015
© Juan Felipe Araneda Arango 2015

Abstract
Organic molecules featuring extended π-conjugated systems have emerged in the last
decade as promising materials for organic based devices. Among these π-conjugated molecules,
ladder-type systems (materials with flat and rigid skeletons) are one of the most interesting
candidates because the annelation eliminates conformational disorders, leading to attractive
photophysical and electronic properties, such as intense luminescence and high carrier mobility.
To further improve the photophysical properties of these materials several main group elements
have been incorporated into these ladder-type structures. These elements impart interesting
features such as more effective orbital interactions, diversity in coordination numbers, and
intriguing structural motifs that can be used to tune properties. Boron is an attractive main group
element that has been used to prepare fascinating π-conjugated materials with potential
application in optoelectronics. Arguably the most important characteristic of a three-coordinate
boron center is the empty p-orbital, which allows effective conjugation of organic π-systems with
and through boron. Furthermore, the exchange of carbon for the more electropositive boron can
also alter the electronic characteristics of a compound significantly.
This thesis focused on the design and development of new boron-containing heterocycles
and their photophysical and electronic properties. Interestingly, these remarkable boron-
containing polycyclic aromatic hydrocarbons can act as strong electron acceptors and it was
possible to isolate and characterize their mono- and di-reduced species. Furthermore, the
reactivity of these molecules towards small molecules such as carbon monoxide and carbon
dioxide was also investigated.
ii
Acknowledgements
I would like to thank Prof. Warren Piers for his guidance through this degree. It has been
a long journey for me and your professionalism and your honesty have left a lasting impression.
Thank you also for helping me to find the right direction in this project and in my formation as a
scientist.
Many thanks are extended to members of my defence committee: Dr. Thomas
Baumgartner, Dr. Belinda Heyne, and Dr. Ray Turner for reading my thesis, offering comments
and taking part in my examination. Thanks to Dr. Milton Smith from Michigan State University
who served as my external examiner.
During this time in the Piers group I have had the opportunity to work with very talented
chemist. There is no point to name all of them, but I would like to particularly thank Dr. Erin
Leitao, Dr. Rich Burford, Dr. Benedikt Neue and Dr. Lauren Mercier, for all your support,
especially at the beginning of this journey. Rich has been a fantastic labmate and friend since my
first year in Calgary, I really appreciate all your help during this time and I hope our paths cross
again. Thanks to Lauren Doyle, Joel Smith, Rich Burford and Matt Morgan for proofreading
different parts of this thesis. I would also like to thank all my friends in Calgary, which made this
journey easier.
Technical support has been very important through this period and I would also like to
thank the technical stuff in this Department. Thank you Bonnie and Jan for keeping me
organized. I am also grateful to the University of Calgary, the Department of Chemistry and
Alberta Innovates Technology Futures for the financial support during my studies.
iii
Finally, I would specially thank my fantastic family. Particularly, my parents Miguel and
Zoraida, my brother Jose Miguel, and my grandmother Liliana. Your support even at the distance
has been invaluable. I deeply thank Pamela, your love, support, and happiness through this
process kept me strong to continue, even in the most difficult times. Thanks for making this
journey together, it was not easy, but we made it…y ahora somos tres!!
iv
Table of Contents
Abstract ............................................................................................................................... ii
Acknowledgements ............................................................................................................ iii
Table of Contents ................................................................................................................ v
List of Tables.................................................................................................................... viii
List of Figures .................................................................................................................... ix
List of Schemes ................................................................................................................ xiii
List of Symbols, Abbreviations and Nomenclature .......................................................... xv
Note on Numbering Scheme ........................................................................................... xvii
CHAPTER ONE: INTRODUCTION ................................................................................. 1

1.1 Main group element-containing π-systems ............................................................... 1
1.1.1 Polycyclic aromatic hydrocarbons and ladder compounds............................... 2
1.2 Boron as the key element for the design of new molecules ...................................... 5
1.3 Boron-containing heterocycles.................................................................................. 6
1.3.1 Boroles .............................................................................................................. 7
1.3.2 Borabenzenes .................................................................................................... 9
1.3.3 Borepins .......................................................................................................... 13
1.4 Aromaticity and antiaromaticity ............................................................................. 15
1.4.1 NMR Chemical Shifts ..................................................................................... 17
1.5 Thesis goals ............................................................................................................. 19
CHAPTER TWO: TOWARDS THE SYNTHESIS OF BENZOBOROLE-FUSED

BENZOBOROLE DERIVATIVES: THE PHOTOCHEMICAL ROUTE.............. 20
2.1 Introduction ............................................................................................................. 20
2.1.1 Previously reported benzoborole-fused benzoheteroles ................................. 20
2.2 Synthetic strategies.................................................................................................. 24
2.3 Synthesis of 1,2-bis(2-(chloro(aryl)boryl)phenyl)ethyne precursors ...................... 25
2.4 Reduction of 1,2-bis(2-(chloro(aryl)boryl)phenyl)ethynes. Synthesis of
dibenzodiboracyclobutylidenes ............................................................................. 30
2.4.1 X-ray crystallography ..................................................................................... 33
2.4.2 Nuclear Magnetic Resonance (NMR) Spectroscopic Analysis ...................... 36
2.5 Photochemical Isomerization. Synthesis of the first benzoborole-fused benzoborole
derivative ............................................................................................................... 39
2.5.1 X-ray crystallography ..................................................................................... 43
2.5.2 Nuclear Magnetic Resonance (NMR) Spectroscopy Analysis ....................... 44
2.5.3 Absorption Spectroscopy ................................................................................ 47
2.5.4 Aromaticity and antiaromaticity. Nucleus Independent Chemical Shift (NICS)
Calculations ..................................................................................................... 48
2.5.5 Electrochemical Studies .................................................................................. 51
2.6 Proposed Mechanism of Photoisomerization .......................................................... 53
2.7 Summary and Conclusions ...................................................................................... 56
CHAPTER THREE: BRØNSTED ACID-CATALYZED SKELETAL

REARRANGEMENTS IN POLYCYCLIC CONJUGATED BORACYCLES: A
THERMAL ROUTE TO BENZOBOROLE-FUSED BENZOBOROLES ............. 57
v
3.1 Introduction ............................................................................................................. 57
3.1.1 Isomerization of the carbon analogue ............................................................. 57
3.2 Chemical reduction of compounds 2-4Tip and 2-5Tip .............................................. 60
3.2.1 One-electron chemical reduction .................................................................... 61
3.2.1.1 EPR Characterization ............................................................................ 62
3.2.1.2 X-ray crystallography............................................................................ 66
3.2.2 Two-electron chemical reduction ................................................................... 68
3.2.2.1 Nuclear Magnetic Resonance (NMR) Spectroscopic Analysis ............ 69
3.3 Absorption and Fluorescence Spectroscopy ........................................................... 78
3.4 Aromaticity and antiaromaticity. Nucleus Independent Chemical Shift (NICS)
Calculations ........................................................................................................... 80
3.5 Thermal Isomerization ............................................................................................ 82
3.5.1 Proposed mechanism ...................................................................................... 88
3.6 Summary and Conclusions ...................................................................................... 91
CHAPTER FOUR: BOROLE RING-EXPANSION BY ADDITION OF CO AND CO293

4.1 Introduction ............................................................................................................. 93
4.2 Addition of carbon dioxide and characterization of insertion products .................. 96
4.2.1 UV-Vis and florescence spectroscopy .......................................................... 104
4.2.2 Proposed mechanism of the carbon dioxide insertion .................................. 105
4.3 Addition of carbon monoxide and characterization of insertion product ............. 107
4.3.1 4.4 UV-Vis and fluorescence spectroscopy .................................................. 112
4.3.2 Molecular Orbital (MO) Calculations........................................................... 115
4.3.3 Proposed mechanism of the carbon monoxide insertion .............................. 116
4.4 Summary and Conclusions .................................................................................... 119
CHAPTER FIVE: CONCLUSIONS AND FUTURE WORK ....................................... 120

5.1 Conclusions ........................................................................................................... 120
5.2 Future Work .......................................................................................................... 122
5.2.1 Intermetallic Communication in Organometallic Complexes ...................... 122
5.2.2 Development of new boron-containing heterocycles ................................... 126
5.2.3 BoraBINOL complexes ................................................................................ 128
CHAPTER SIX: EXPERIMENTAL DETAILS ............................................................. 131

6.1 General Considerations ......................................................................................... 131
6.1.1 Laboratory Equipment .................................................................................. 131
6.1.2 Solvents ......................................................................................................... 131
6.1.3 Instrumentation ............................................................................................. 132
6.1.4 Starting Materials .......................................................................................... 134
6.2 Experimental Details for Chapter 2....................................................................... 135
6.2.1 Synthetic Procedures..................................................................................... 135
6.2.2 Photoisomerization Details ........................................................................... 141
6.3.2 EPR Spectroscopy......................................................................................... 148
6.3.2.1 Titration Experiment ........................................................................... 150
vi
REFERENCES ................................................................................................................ 153
APPENDIX A: CRYSTALLOGRAPHIC DATA .......................................................... 163
APPENDIX B: THEORETICAL CALCULATIONS .................................................... 204
APPENDIX C: LIST OF PUBLICATIONS ................................................................... 223
APPENDIX D: COPYRIGHT PERMISSION ............................................................... 224
vii
List of Tables
Table 2-1 Selected Metrical Data for 2-3Tip .................................................................................. 29
Table 2-2 Selected bond distances (Å) and angles (°) for 2-4Tip .................................................. 34
Table 2-3 Selected bond distances (Å) and angles (°) for 2-5Tip .................................................. 44
Table 2-4 NICS (1/0) and NICS(1)zz values for 2-5Tip ................................................................. 49
Table 2-5. Borole NICS(1)zz values for compounds 2-VII – 2-VIII and 2-5Tip ........................... 50
Table 2-6 NICS (1/0) and NICS(1)zz values for 2-4Tip ................................................................. 51
Table 3-2 Electrochemical data for 2-4Tip and 2-5Tip .................................................................... 61
Table 3-3 Calculated and simulated ∣hfcc∣ of 3-2Tip and 3-3Tip (in gauss) ................................. 65
Table 3-7 NICS (1/0) values for 2-5Tip, 3-6Tip and 3-III .............................................................. 81
Table 4-1 Selected Metrical Data for 4-1Tip ................................................................................ 102
Table 4-2 Selected Metrical Data for 4-2Tip ................................................................................ 111
viii
List of Figures
Figure 1-1 Calculated electronic structures of parent polyheteroles. .............................................. 2
Figure 1-2 (E)-stilbene (1-I), methylene bridged stilbene (1-II) and pentacene ............................ 3
Figure 1-3 Ladder compounds containing the thiophene unit......................................................... 4
Figure 1-4 Functional features of boron.......................................................................................... 6
Figure 1-5 Anthacene (left) and boraanthacene (right) ................................................................... 6
Figure 1-6 Boron-containing heterocycles ...................................................................................... 7
Figure 1-7 Several borole derivatives ............................................................................................. 8
Figure 1-8 Dibenzoborole and benzoborole-fused benzoheteroles compounds ............................. 9
Figure 1-9 Polycyclic aromatic hydrocarbons containing a BN moiety reported by Piers ........... 11
Figure 1-10 Examples of aromatic and antiaromatic compounds ................................................. 17
Figure 1-11 Magnetic shielding lines for benzene ........................................................................ 18
Figure 1-12 NICS values for benzene. Calculations were performed at B3LYP/6-311+G(d)
level ....................................................................................................................................... 19
Figure 2-1 Thermal ellipsoid (50%) diagrams of the molecular structure of 2-3Tip. Hydrogen
atoms have been removed for clarity .................................................................................... 29
Figure 2-2. 1H and 11B NMR spectra of the product of the reaction between KC8 and 2-3Mes
(CD2Cl2, 400 MHz) ............................................................................................................... 32
Figure 2-4 Thermal ellipsoids (50%) diagram showing packing motif in 2-4Tip .......................... 36
Figure 2-5 1H NMR spectrum of 2-4Tip (CD2Cl2, 600 MHz, 293 K)............................................ 37
Figure 2-6 13C{1H} NMR spectrum of 2-4Tip (CD2Cl2, 150 MHz, 293 K) .................................. 38
Figure 2-7 UV-Vis and fluorescence spectra of 2-4Tip measured in CH2Cl2 (10-4 M).................. 40
Figure 2-8 Photochemical reaction of 2-4Tip monitored by 1H NMR spectroscopy (irradiated

in a quartz NMR tube at 254 nm). The top spectrum corresponds to the 1H NMR
spectrum of 2-4Tip prior to irradiation; the middle traces are the spectra at partial
conversion, with the peaks marked by the * due to the intermediate; the bottom is the
ix
spectrum after full conversion to 2-5Tip. a = solution of 2-4Tip; b = solution of 2-4Tip
under UV light (254 nm); c = solution of 2-5Tip.................................................................... 41
atoms have been removed for clarity. ................................................................................... 43
Figure 2-10 1H NMR spectrum of 2-5Tip (CD2Cl2, 600 MHz, 293 K).......................................... 46
Figure 2-11 Chemical shift of isopropyl methine protons ............................................................ 46
Figure 2-12 13C{1H} NMR spectrum of 2-5Tip (CD2Cl2, 600 MHz, 293 K) ................................ 47
Figure 2-13 UV-Vis absorption spectrum of 2-5Tip measured in CH2Cl2 (10-4 M) ...................... 48
Figure 2-14 Left: cyclic voltammetry traces for 2-4Tip. Right: cyclic voltammetry traces for
2-5Tip (insert corresponds to the reversible wave when potential does not exceed –1.75
V). Cyclic voltammetry was carried out at a scan rate of 100 mV/s in THF with 1mM
substrate and 0.1M [NBu4][PF6] as the supporting electrolyte. Ferrocene was added as
an internal standard. .............................................................................................................. 52
Figure 2-15 Molecular orbitals relevant for the photoreaction: HOMO-6, HOMO, LUMO,
LUMO+2 (isocontour value 0.02), oscillator strength, and wavelength ............................... 53
Figure 3-1 Thermal ellipsoid (50%) diagram of the molecular structure of 3-1Tip. Hydrogen
Figure 3-2 Overlap of the experimental and simulated EPR spectrum of 3-2Tip (left) and 3-
3Tip (right). SOMO and spin density (UB3PW91/6-31+G(d)) of 3-2Tip (left) and 3-3Tip
(right) ..................................................................................................................................... 63
atoms and Cp*2Co have been removed for clarity ................................................................ 67
Figure 3-4 1H NMR spectrum of compound 3-5Tip (THF-d8, 600 MHz) ..................................... 70
Figure 3-5 Qualitative titration of compound 3-5Tip. The increment in the series numbers
indicate a qualitative increment in the amount of compound 2-4Tip added to the EPR
tube containing 3-5Tip ............................................................................................................ 71
Figure 3-6 11B chemical shifts of several borole dianions ............................................................ 72
Figure 3-7 1H NMR spectrum of compound 3-6Tip (THF-d8, 600 MHz) ..................................... 73
atoms and THF molecules have been removed for clarity .................................................... 74
atoms and THF molecules have been removed for clarity .................................................... 76
x
Figure 3-10 Bond distance (Å) comparison between the borole rings in 2-5Tip and 3-6Tip .......... 78
Figure 3-11 Absorption and emission spectrum of compounds 3-5Tip and 3-6Tip in THF. Blue
line: 3-5Tip absorption; red line: 3-6Tip absorption; dotted red line: 3-6Tip emission. ........... 79
Figure 3-12 HOMO and LUMO orbitals of compounds 3-5Tip and 3-6Tip ................................... 80
Figure 3-13 Several pentalene derivatives and their longest absorption maxima ......................... 80
Figure 3-15 1H NMR spectrum of compound 3-7Tip (CD2Cl2, 600 MHz).................................... 86
Figure 3-16 Isomerization of 3-5Tip to 3-6Tip after addition of 2 equivalents of t-butanol

(THF-d8, 600 MHz). ............................................................................................................. 87
Figure 3-17 Optimized structures of compounds 3-5Tip and 3-6Tip, intermediates IA, IB and
the transition state TS. Hydrogen atoms have been removed for clarity .............................. 90
Figure 4-1 1H NMR spectrum of compound 4-1Tip (CD2Cl2, 600 MHz).................................... 100
Figure 4-2 Truncated predicted isotopic distribution and MALDI-TOF spectrum of 4-1Tip ...... 100
Figure 4-3 Thermal ellipsoid (50%) diagram of the molecular structure of 4-1Tip. Hydrogens,
potassium atoms and THF molecules have been removed for clarity................................. 102
Figure 4-4 POV-ray depiction of 4-1Tip. Hydrogen atoms and THF molecules have been
removed for clarity. C: gray, B: orange, O: red, K: purple. ................................................ 103
Figure 4-5 Absorption spectrum of compound 4-1Tip in CH2Cl2 ................................................ 104
Figure 4-6 Emission spectrum of compound 4-1Tip in CH2Cl2 ................................................... 105
Figure 4-7 Addition of carbon monoxide to 3-6Tip (70 ºC, THF-d8, 600 MHz) ........................ 109
atoms and THF molecules have been removed for clarity .................................................. 111
Figure 4-9 POV-ray depiction of 4-2Tip. Hydrogen atoms have been removed for clarity. C:
gray, B: orange, O: red, K: purple. ...................................................................................... 112
Figure 4-10 Absorption spectrum of compound 4-2Tip in THF .................................................. 113
Figure 4-11 Jablonski diagram showing absorption and emission of photons. Reprinted by
permission from Macmillan Publishers Ltd: Nat. Methods 2005, 2, 910, copyright 2005 . 114
Figure 4-12 Emission spectrum of compound 4-2Tip in THF ..................................................... 115
xi
Figure 4-13 Calculated HOMO (left) and LUMO (right) of 4-2Tip (B3LYP/6- 311G(d)) ......... 116
Figure 5-1 Organometallic polymer ............................................................................................ 123
Figure 5-2 Classification of mixed-valence systems according to Robin and Day’s rule .......... 124
Figure 5-3 4-1Tip and BINOL compounds .................................................................................. 129
Figure 5-4 Heterobimetallic multifunctional catalyst using cerium............................................ 129
Figure 6-1 Photochemical reaction of 2-4Tip monitored by 1H NMR spectroscopy. Alkyl

region (top) and aromatic region (bottom) .......................................................................... 142
Figure 6-2 Experimental (black) and simulated (red) EPR spectrum of 3-2Tip (top).
Experimental (black) and simulated (red) EPR spectrum of 3-3Tip (bottom) ..................... 149
indicate a qualitative increment in the amount of compound 2-4Tip added to the EPR
tube containing 3-5Tip. ......................................................................................................... 150
xii
List of Schemes
Scheme 1-1 Synthesis of benzoheterole-fused benzoheterole derivatives ...................................... 4
Scheme 1-2 Synthesis of benzosilole-fused benzosilole derivatives .............................................. 4
Scheme 1-3 Synthesis of pentaphenylborole .................................................................................. 8
Scheme 1-4 Synthesis of neutral borabenzene .............................................................................. 10
Scheme 1-5 Synthesis of BN-phenanthrene .................................................................................. 11
Scheme 1-6 Synthesis of boraacene derivatives ........................................................................... 12
Scheme 1-7 Synthesis of borepin derivatives ............................................................................... 13
Scheme 1-8 Synthesis of pentacyclic borepins ............................................................................. 15
Scheme 2-1 Formation of benzoborate-fused benzophosphonium derivatives ............................ 21
Scheme 2-2 Synthesis benzoborole-fused benzothiophene 2-IV .................................................. 23
Scheme 2-3 Synthesis of benzoborole-fused benzoheterole derivatives ...................................... 23
Scheme 2-4 Feasible routes to prepare the target benzoborole-fused benzoborole derivative ..... 25
Scheme 2-5 Synthetic route to prepare compounds 2-3Ar............................................................. 26
Scheme 2-6 Reaction of compounds 2-3Ar with KC8 ................................................................... 30
Scheme 2-8 Synthesis of benzoborole-fused benzoborole 2-5Tip ................................................. 42
Scheme 2-9 Synthesis of 1,9-dimethyldibenzo[b,f]pentalene dication ......................................... 42
Scheme 2-10 Proposed mechanism for the formation of 2-5Tip; path a involves photocleavage
of B-C bond a, path b, bond b. Numbers in square brackets indicate the energies (kcal
mol-1) of the species shown relative to 2-4Tip (SCS-MP2/6-311+G(d,p)//B3LYP/6-
31G(d)+ZPE149). .................................................................................................................... 55
Scheme 3-1 Proton catalysed isomerization of 1,1’-bis(benzocyclobutylidene) (3-I).................. 58
Scheme 3-2 Formation of 3-1Tip ................................................................................................... 58
Scheme 3-3 Proposed thermal pathway for the synthesis of 2-5Tip .............................................. 60
Scheme 3-4 Synthesis of radical anions 3-2Tip, 3-3Tip and 3-4Tip ................................................. 62
Scheme 3-5 Synthesis of 3-5Tip and 3-6Tip .................................................................................... 68
xiii
Scheme 3-6 Isomerization of 3-5Tip to 3-6Tip, synthesis of 3-7Tip and generation of 2-5Tip via
oxidation of 3-6Tip ................................................................................................................. 83
Scheme 3-7 Proposed mechanism for the rearrangement of 3-5Tip. Numbers in brackets
indicate the energies (kcal mol-1) of the species relative to IA (in black) and 3-5Tip (in
gray) (SCS-MP2/6-311+G(d,p)//B3LYP/6-31G(d)+ZPE).................................................... 89
Scheme 4-1 Ring-expansion of pentaphenylborole ...................................................................... 93
Scheme 4-2 Synthesis of azaborinines via ring-expansion of borole derivatives ......................... 94
Scheme 4-3 Dutton’s proposed mechanism for the formation of 1,2-azaboririne product ........... 95
Scheme 4-4 Reaction of pentaarylboroles with carbon monoxide ................................................ 96
Scheme 4-5 Synthesis of 4-1Tip ..................................................................................................... 98
Scheme 4-6 Proposed mechanism for the formation of 4-2Tip from 3-5Tip and 3-6Tip................ 107
Scheme 4-7 Synthesis of 4-2Tip ................................................................................................... 108
Scheme 4-8 Plausible mechanism for the formation of 4-2Tip .................................................... 118
Scheme 5-1 Graphical Thesis Summary ..................................................................................... 121
Scheme 5-2 Aromatic ligands and some iron bimetallic complexes .......................................... 124
Scheme 5-3 Proposed synthesis of bimetallic systems containing the benzoborole-fused

benzoborole framework....................................................................................................... 125
Scheme 5-4 Synthetic route reported for V-1Ph .......................................................................... 127
Scheme 5-5 Proposed synthetic route to borataindenofluorene derivatives ............................... 128
xiv
List of Symbols, Abbreviations and Nomenclature
Symbol Definition
Å Angstrom
Anal Calcd Calculated (elemental) analysis
Ar Aryl group
B3LYP Becke three parameter Lee-Yang-Parr
ca. Circa (approximately)
ºC Celsius
d Doublet
DFT Density Functional Theory
E1/2 Half-wave reduction/oxidation potential
equiv Equivalents
ESI-MS Electrospray ionization mass spectrometry
f Oscillator strength
g Gram(s)
GC-MS Gas chromatography – mass spectrometry
h (Hours)
HMBC Heteronuclear Multiple Bond Coherence
HOMO Highest occupied molecular orbital
Hz Hertz
i
Pr Isopropyl
J Symbol for scalar coupling constant
K Kelvin
LUMO Lowest occupied molecular orbital
M Molarity (mol L-1)
m meta
m multiplet
MALDI MS Matrix Assisted Laser Desorption Ionization mass
spectrometry
Me Methyl
MHz Megahertz
mL millilitre
min minute(s)
mmol millimol(s)
NICS Nucleus Independent Chemical Shift
NMR nuclear magnetic resonance
o ortho
o/n overnight
p para
Ph phenyl
ppm parts per million
q quartet
R alkyl group
rt room temperature
s singlet
xv
So Photophysical ground state
SX Photophysical xth singlet excited state
sp septet
T temperature
t triplet
TD-DFT Time Dependent-Density Functional Theory
Tip 2,4,6-triisopropylphenyl
THF tetrahydrofuran
t-Bu tertiary-butyl (-C(CH3)3)
UV Ultraviolet
Vis visible
xs excess
º degree(s)
n
JX-Y n (e.g. 1, 2, 3,….) bond coupling between atoms X
and Y
1D one dimensional
2D two dimensional
δ chemical shift
ε Molar absorptivity
Φ fluorescence quantum yield
λ wavelength
ν wavenumbers
{1H} proton decoupled
xvi
Note on Numbering Scheme
Novel compounds prepared in Chapters two, three and four were denoted as “X-#” where
X represents the chapter number and # was given in chronological order. The first compound in
Chapter two was therefore denoted “2-1”. Chronological numbers were used as the compounds
were introduced in the text. Previously synthesized materials presented in the Introduction
sections of Chapters two, three and four were numbered “X-#’” where X represented the chapter
number and # was a Roman numeral given in chronological order. To represent different groups
attached to the boron center, the numbering scheme became “X-#group.
xvii
Chapter One: Introduction
1.1 Main group element-containing π-systems
Incorporation of main group elements into organic π-frameworks has emerged in the last
decade as a promising route to develop new materials and compounds with interesting properties
not observed in the all-carbon analogues.1-4 The main group element allows for the tuning of the
photophysical and electronic properties of the new molecules because it allows access to new
electronic levels mainly due to their favourable orbital overlap with the π-system.5 For example,
Lagowski reported a series of calculations of polyheteroles containing various main group
elements5,6 that showed that the electronic structure of the polymers highly depends on the main
group element (Figure 1-1). Several research groups are exploiting this orbital interaction by
preparing new π-conjugated systems, commonly incorporating of elements such as B,7-9 Si,5,10,11
P,12-14 or S15-17 into π-conjugated systems.
1
Figure 1-1 Calculated electronic structures of parent polyheteroles5,6
1.1.1 Polycyclic aromatic hydrocarbons and ladder compounds
Polycyclic aromatic hydrocarbons, particularly the linear acenes, have garnered
considerable interest due to their potential as organic semiconducting materials.1,18 These fused
aromatic compounds have been used to fabricate electronic transistor19,20 and light-emitting
diode devices,21 while substituted derivatives of the pentacene framework have been explored as
an acceptor material in bulk heterojunction solar cells.22,23 “Ladder” compounds (molecules with
flat rigid polycyclic skeletons) are attractive because, as acene analogues, they are planar
molecules and possess an extended π-conjugated system.24 This leads to exceptional
photophysical and electrochemical properties including intense luminescence and high charge
carrier mobility.1,2
2
H2
C
C
H2
1-I 1-II Pentacene
Figure 1-2 (E)-stilbene (1-I), methylene bridged stilbene (1-II) and pentacene
For instance, (E)-stilbene (1-I) has a fluorescence quantum yield of 0.05 at room
temperature; however, its methylene bridged derivative (1-II) has a fluorescence quantum yield
close to unity.25 Clearly the restriction of the rotation around the aryl rings reduces the energy
loss via vibrational relaxation and increases the emission efficiency.26 There are several
strategies to modify the electronic and photophysical properties of these ladder compounds, two
of which are extension of the π-system and ring closure. In the last decade there has been an
increased interest by the scientific community in the incorporation of main group elements into
organic frameworks to enhance their properties due to their aforementioned photophysical and
electronic properties. The first ladder derivatives containing main group elements were reported
by Sashida in 1995.27 2,2’-di-bromophenyl acetylene was lithiated with t-BuLi in THF, followed
by addition of the desired element as a powder. After the workup, the air and moisture stable
compounds were isolated as yellow (1-III) or white (1-IV and 1-V) solids with yields ranging
from 49 to 55% (Scheme 1-1). That report only dealt with the synthesis of the compounds and no
further studies were reported. More than 10 years later, Takimiya explored the properties of the
thiophene derivative and showed that after addition of alkyl chains to the benzene rings the
molecule became a promising candidates for air-stable organic semiconductors.28 Subsequently,
the Takimiya group also explored modifications to the thiophene ladder compound such as
3
increasing the number of aromatic rings, the symmetry of the molecules and the substitution of
more benzene rings for thiophene units (Figure 1-3).29,30
Br
E 1-III: E = S
1) t-BuLi
1-IV: E = Se
2) E 1-V: E = Te
E
Br
Scheme 1-1 Synthesis of benzoheterole-fused benzoheterole derivatives27
S
S
S
S
S
S
S
S
S
S
Figure 1-3 Ladder compounds containing the thiophene unit29,30
Tamao reported the synthesis of benzosilole-fused benzosilole derivatives based on a new
intramolecular reductive cyclization.25 In this strategy, lithium naphthalenide (LiNaph) reduces
the acetylene moiety in 1-VIa-b, producing a dianionic intermediate, which undergoes
cyclization to produce 1-VIIa-b (Scheme 1-2).
R
X Si R R R
Si
1) 4 LiNaph, THF Si
Si
2) I2 Si
R Si X R R Si
Si
R
1-VIa: R = Me, X = H 1-VIIa: R = Me 1-VIII
1-VIb: R = Ph, X = H 1-VIIb: R = Ph
Scheme 1-2 Synthesis of benzosilole-fused benzosilole derivatives25
4
An excess of reducing agent is required because the resulting benzosilole-fused
benzosilole has a slightly lower reduction potential than the starting material, consuming some
amount of the reductant. The over-reduced bridged stilbene is oxidized to the desired product
with an iodine workup. The products are isolated as white solids with fluorescence quantum
yields close to 0.6. Compared to the all-carbon analogues, compounds 1-VIIa-b have an intense
blue emission that is red-shifted about 60 nm.25 Interestingly, this methodology can be applied to
the synthesis of a more extended analogue 1-VIII. This compound is planar, with a dihedral
angle between the central and the outer benzene rings of 3.9°. This planarity, along with the bond
distances, suggests that there is an effective π-conjugation through the entire framework.
1.2 Boron as the key element for the design of new molecules
Boron is one of the main group elements that has attracted more attention in recent
years.7,8 In a three-coordinate boron center, the empty p-orbital allows effective conjugation of
organic π-systems throughout the whole system (Figure 1-4 (a)), and it also allows coordination
of Lewis bases (Figure 1-4 (b)).31 Furthermore, due to the vacant p-orbital, boron is inherently
electron poor. It could be considered a strong π-electron acceptor, but it may also act as a sigma-
donor due to its lower electronegativity compared to carbon.32 Following the pioneering studies
of Williams and Kain,33-35 boryl groups have widely been used as π-electron accepting units and
nowadays they are promising candidates to prepare fascinating π-conjugated materials.8,36,37
5
N B N B Nu B
(b)
(a)
Figure 1-4 Functional features of boron
The transposition of carbon for the more electropositive boron atom can also alter the
HOMO–LUMO characteristics of a compound significantly. For example, our group has found
that 9-boraanthracene, stabilized by an N-heterocyclic carbene,38 unlike anthracene itself,
absorbs in the visible region because the HOMO–LUMO gap is strongly decreased compared to
its all-carbon analogue (Figure 1-5). The same effect was found in the more extended
boratetracene and borapentacenes analogues.39
B
NHC
HOMO: –5.7 eV HOMO: –4.1 eV
LUMO: –2.5 eV LUMO: –1.9 eV
Figure 1-5 Anthacene (left) and boraanthacene (right)38
1.3 Boron-containing heterocycles
Apart from the promising materials that can be prepared with boron-containing
molecules, boron-containing heterocycles are of fundamental interest and have been used for
6
decades to help us to understand fundamental, yet ubiquitous, concepts in chemistry, such as
Lewis acidity/basicity and aromaticity/antiaromaticity. For instance, boron is isoelectronic with a
carbocation; therefore the boron-containing unsaturated five-membered ring, borole, is
isoelectronic to the elusive antiaromatic 4 π-electron cyclopentadienyl cation, for which no
simple derivative has been isolated or structurally characterized so far.40-42 The most studied
boron-containing heterocycles are the boroles, borabenzenes and borepins, which are five-, six-
and seven-membered heterocycles respectively (Figure 1-6).
B B B
Borole Borabenzene Borepin
Figure 1-6 Boron-containing heterocycles
1.3.1 Boroles
Eisch reported the synthesis of the first borole derivative in 1969 as shown in Scheme
1-3.43 The original synthesis relied on two methods to prepare pentaphenylborole: (a) by direct
reaction of 1,4-dilithio-1,2,3,4-tetraphenylbutadiene44 with phenyldibromoborane, and (b) by
boron–tin exchange between the 2,3,4,5-tetraphenylstannole derivative with
phenyldichloroborane. As expected, this blue compound was highly air and moisture sensitive
and reacted with Lewis bases. The phenyl substituents are required in order to stabilize the
borole unit, as sterically less congested boroles such as PhB4C4Me4 undergo dimerization via a
Diels–Alder reaction.45,46
7
PhBCl2 PhBBr2
Sn B
Li Li
Scheme 1-3 Synthesis of pentaphenylborole43
After that seminal report the chemistry and reactivity of boroles was sparsely explored
for almost four decades. The elucidation of the solid-state structure of the original Eisch’s
pentaphenylborole by the Braunschweig group in 2008 and the development of improved
synthetic routes to new borole derivatives has revitalized this chemistry in the last couple of
years. In this context, several fascinating borole derivatives have been reported in the past few
years, such as borole metal complexes,47,48 tetrathienyl-substituted boroles,49 carbene-
coordinated boroles50,51 and highly Lewis acidic perfluorinated boroles (Figure 1-7).52-54 Some of
these compounds have shown very interesting properties and reactivity. For instance,
perfluorophenylborole reported by Piers52 can activate hydrogen under metal-free conditions.55
C6F5 C6F5 F
F
L C6F5
Cl Pt B F
C6F5 B C6F5
L B C6F5
C6F5 F
C6F5
Ph Ph
K
S S
Ph B Ph
S S
B Mes N N Mes
Mes
Figure 1-7 Several borole derivatives52-54
8
Furthermore, the borole unit has also been incorporated into π-systems in order to
determine the participation of the empty p-orbital in the conjugation of electrons and the effect of
fused rings into the antiaromatic character of borole. In 2002, Tamao reported the synthesis of a
series of dibenzoborole derivatives, such as 1-IX, and showed that the fused benzene rings
helped to stabilize the borole unit.56 They also observed that the presence of the benzene rings
decreased the antiaromaticity of the systems.57 Several other benzoborole-fused benzoheteroles,
such as the ones shown in Figure 1-8 have also been reported; they will be discussed in more
detail in the introduction of Chapter two.
Tip Mes
B B E = NMe
E=O
E=S
E
1-IX
Figure 1-8 Dibenzoborole and benzoborole-fused benzoheteroles compounds56
1.3.2 Borabenzenes
Historically, the chemistry of anionic borabenzenes (boratabenzenes) has been explored
in considerably more detail than the neutral borabenzenes.58-61 Most likely the lack of a facile
synthetic route to prepare borabenzenes influenced the scarcity of research around this benzene
analogue.62-65 However, in 1998, Fu reported an efficient and general route to the neutral
9
borabenzenes (Scheme 1-4), revitalizing the study of the neutral borabenzenes.62* Treatment of
commercially available (1-trimethylsilyl)-1,4-pentadiyne with dibutylstannane afforded the
stannacycle, which subsequently underwent a transmetallation after exposure to BCl3 to produce
the chloroboracycle. Exposure of the boracycle to a Lewis base resulted in the elimination of
Me3SiCl, to provide the borabenzene-Lewis base adduct. Some of the Lewis bases tested were
pyridine, 2,6-lutidine, triethylamine, and triphenylphosphine. The conversion of the boracycle to
the borabenzene proceeds via base-catalyzed isomerization, followed by ligand-induced
elimination of Me3SiCl. In order to successfully perform the reaction, the Lewis base must be
relatively strong, as weaker bases such as dialkyl ethers or aldehydes failed to effect the
reaction.66 Using this method, more complex molecules containing the borabenzene unit have
also been prepared by Piers (top compounds in Figure 1-9).67,68
SiMe3
pyridine
2,6-lutidine
B L L = NEt
3
PMe3
+L
H2SnBu2
– ClSiMe3
SiMe3 SiMe3 SiMe3

Bu BCl3
Sn B Cl B Cl
Bu – Cl2SnBu2
Scheme 1-4 Synthesis of neutral borabenzene62
*
This synthesis is a modification of the synthesis previously reported by Schmid (Boese, R.; Finke, N.; Keil, T.;
Paetzold, P.; Schmid, G. Z. Naturforsch. (B) 1985, 40, 1327). Some of the modifications reported by Fu involve the
incorporation of the TMS group in the starting diyne (instead of adding it latter in the synthesis) and the formation
of the borabenzene adduct from the chloroboracycle instead of its methoxy analogue). The modifications allowed to
improve the overall yield of the pyridine adduct by a factor of five and to synthesize the compounds in multigrams
scale.
10
top
B B
N N B B
N N
bottom
N N
N
B B
N B B
Figure 1-9 Polycyclic aromatic hydrocarbons containing a BN moiety reported by Piers69-71
Piers et al. have subsequently exploited this sequence of reactions
(isomerization/elimination) in order to prepare polycyclic aromatic hydrocarbons containing a
BN moiety such as the compounds shown in the bottom of Figure 1-9.69-71 The general procedure
is illustrated in Scheme 1-5 for the synthesis of BN-phenanthrene.69 Following the base-
catalyzed isomerization to form the BN adduct, there is a facile cycloisomerization of the
pendent ethynyl group, a transformation that is well-known in all-carbon aromatic compounds
and other heteroaromatic systems.72,73†
SiMe3
+ N B
B – ClSiMe3 N B
Cl N
Scheme 1-5 Synthesis of BN-phenanthrene69
†
The all-carbon systems typically require a soft metal catalyst, UV irradiation, or flash vacuum pyrolysis.
11
Our group has also prepared several π-extended borabenzene analogues.39,74 The main
strategy in the synthesis of such challenging molecules was to stabilize the boron center with a
strong donor and to subsequently deprotonate the heterocyclic ring with a strong base (this
sequence is illustrated in Scheme 1-6 using 9-bora-9-chloro-9,10-dihydroanthracene as the
starting material). Several Lewis bases such as pyridine, lutidine and DABCO (1,4-
diazabicyclo[2.2.2]octane) were used in order to stabilize the boron center. All of them achieved
that purpose; however, spontaneous elimination of HCl or deprotonation using a base was never
observed, even at elevated temperatures.75 N-heterocyclic carbenes are strong neutral donors and
can provide good steric protection of the boron center to prevent nucleophilic attack of the base.
H2IMes (1,3-bis(2,4,6-tri-methyl)imidazolidin-2-ylidene) proved to be the right base in order to
stabilize the boron center and facilitate the deprotonation of the heterocyclic ring with LiTMP
(lithium tetramethylpiperidide) as shown in Scheme 1-6.74 Using the same protocol the π-
extended analogues 5-boratetracene, and 6-borapentacene were also prepared.39 As mentioned
before, all these boraacenes showed a smaller HOMO-LUMO gap compared to the carbon
analogues.
H H H H
H2IMes LiTMP
B B B
Cl H2IMes H2IMes
Cl
B B
H2IMes H2IMes
Scheme 1-6 Synthesis of boraacene derivatives74
12
1.3.3 Borepins
Seven-membered boron containing heterocycles are commonly known as borepins. Even
though these compounds have been known for several decades,76-79 they were not explored in
much detail until a few years ago. In 2009 Piers reported the synthesis and characterization of
benzo- and naphthoborepins.80 The synthesis is illustrated in Scheme 1-7 for the preparation of
benzoborepin, but by using the appropriate starting material benzo- and naphthoborepins can be
prepared in moderate yields following the same procedure. Direct quenching after lithiation of
the dibromo-stilbene derivative with boron reagents such as MesBCl2 or MesB(OMe)2 (Mes =
1,3,5-trimethylbenzene) were not successful. Therefore, the authors took advantage of the boron-
tin exchange81,82 by quenching the resulting dianionic species with Me2SnCl2. The seven-
membered stannacycle was readily converted to the targeted borepin by addition of BCl3,
followed by treatment with MesLi. The borepin derivatives were stable enough towards air and
moisture to be purified by column chromatography.
Br Br
1) n-BuLi 1) BCl3
2) Me2SnCl2 Sn 2) MesLi B
Me Me Mes
Mes =
B B
Mes Mes
Scheme 1-7 Synthesis of borepin derivatives80
13
Tovar has also investigated the properties of borepin derivatives. In 2010, his group
reported the synthesis of larger fused polycyclic aromatics containing two fused borepin units.83
Similar to the synthesis reported by Piers, the key step in the formation of the para-borepin-
containing polycyclic aromatic compounds was a boron-tin exchange as shown in Scheme 1-8.
The bulky tris(tert-butylphenyl) (“super mesityl”, Mes*) B-substituent rendered very stable
frameworks to ambient conditions. The bulk of the Mes* group even shielded the boron center
from attack by small nucleophiles such as fluoride ions. These compounds were thermally robust
and showed no signs of decomposition after heating at 130 ºC. Interestingly, the authors were
able to perform a Kumada coupling reaction with the chloro derivative 1-Xb in order to produce
aryl-substituted compounds 1-XIa and 1-XIb. As expected the pentacyclic aromatic compounds
1-Xa and 1-Xb displayed a red-shifted absorption (~439 nm) and emission (~456 nm) profile
compared to the borepin reported by Piers (~358 nm). However, no dramatic effect in the
photophysical or electrochemical properties was observed by addition of the pendant aryl groups
to the pentacyclic compounds (compound 1-Xa vs 1-XIa and 1-XIb). Following a similar
synthetic procedure, Tovar also prepared the meta-borepin-containing polycyclic aromatic
compound 1-XII,84 which surprisingly displayed a blue-shifted absorption (~400 nm) and
emission (~421 nm) compared to the para-borepin isomer (1-Xa). This blue shift was attributed
to a longer conjugation pathway in the para-derivative relative to 1-XII.84
14
R Br Br Mes*
Sn R B R
1) sBuLi
Sn 1) BCl3 R B
2) Me2SnCl2 R
Br Br R 2) Mes*Li Mes*
1-IXa (R=H) 1-Xa (R=H)
1-IXb (R=Cl) 1-Xb (R=Cl)
Mes* R' Mes* Mes*

Ni(dppp)2Cl2 B B B
R' MgBr B
R' Mes*
1-XII
1-XIa (R'=Me)
1-XIb (R'=OMe)
Scheme 1-8 Synthesis of pentacyclic borepins84
1.4 Aromaticity and antiaromaticity
The concepts of aromaticity and antiaromaticity have been present (and debated) in the
scientific community for several decades. Despite being used very frequently in scientific
literature, aromaticity and antiaromaticity have no precise and quantitative definition and it is not
possible to measure it directly.40,85 Since both concepts will be used regularly in the following
chapters, a detailed definition and a description of the most common features of aromatic and
antiaromatic systems seems appropriate in this introduction.
Benzene is the paradigmatic example of an aromatic system. As such, several aspects of the
chemistry of benzene are considered hallmarks of aromatic character. Generally, aromaticity is a
special stability provided to a system upon meeting the following criteria:40,85-87
• Cyclic structure. Linear systems are not aromatic, all atoms in the ring must be involved
in the π-system.
15
• Delocalized conjugated π bonds. All atoms in the ring must be involved in the π-system,
so each atom must be either sp2 or sp hybridised. This is usually observed in the
structural parameters determined by X-ray diffraction, where the bonds do not fall
exactly in the range of single, double or triple, but rather somewhere in between.
• Coplanar structure. All the atoms should be in the same plane.
• Hückel's Rule. The systems must have 4n + 2 number of π-electrons, where n=0, 1, 2, 3,
and so on. For instance, benzene has 6 π-electrons.
In contrast to the stability of aromatic systems, planar π-systems with a 4n π-electrons (where
n=1, 2, 3, and so on) are generally observed to be unstable, and molecules meeting these criteria
are called antiaromatic.40 The instability of antiaromatic systems is quite severe and the
molecules will tend to alter their electronic or conformational structure to avoid this situation,
thereby becoming non-aromatic. For instance, cyclooctatetraene (8 π-electrons) distorts itself out
of planarity, breaking the π overlap between adjacent double bonds.88,89 Interestingly, addition of
two electrons would create an aromatic system,90 and indeed reduction to the cyclooctatetrene
dianion leads to a planar structure.88 Likewise, cyclobutadiene adopts a rectangular structure
where there is no resonance and the single bonds are markedly longer than the double bonds.91,92
This distortion has a very low activation barrier, estimated to be 5-10 kcal/mol.86 Figure 1-10
shows common examples of aromatic and antiaromatic molecules.
16
aromatic antiaromatic
Figure 1-10 Examples of aromatic and antiaromatic compounds
1.4.1 NMR Chemical Shifts
As NMR spectroscopy became more accessible for chemists to characterise organic
compounds it was noted that the chemical shifts of arene hydrogens were found downfield
shifted from those of olefins.93 The circulation of electrons within the molecular orbitals that are
above and below the ring (ring current) creates an anisotropic magnetic field (Figure 1-11).86 In
the case of aromatic compounds the ring current creates an induced magnetic field that reinforces
the external magnetic field in the region outside the ring, shifting the proton resonances
downfield (normally in the range of 6 to 8 ppm).94,95 Likewise, in the inside region of the ring,
the induced magnetic field opposes the external magnetic field, which would shift proton
resonances upfield, should they be located in this region of the molecule.96 The upfield shift in
aromatic compounds is called paramagnetic shift, while the downfield shift is called diamagnetic
shift. On the contrary, in antiaromatic compounds the induced magnetic field opposes the
external magnetic field in the region outside of the ring and reinforces the external magnetic field
in the inside region of the ring.
17
External
magnetic field Indiced
shielded magnetic field
region
H H
deshielded deshielded
region H H region
H H
shielded
region
Figure 1-11 Magnetic shielding lines for benzene
Schleyer proposed the use of absolute magnetic shieldings, computed in and above the
ring center at various distances (increments of 1 Å) as a probe for aromaticity or
antiaromaticity.97 “Dummy atoms” are placed in these positions and then nucleus independent
chemical shift values (NICS) are calculated (Figure 1-12). In order to correspond with the
familiar NMR proton chemical shifts, the sign of the computed values are reversed. Negative
NICS values denote aromaticity while positive NICS values are characteristic of
antiaromaticity.85,97 NICS values have become a standard index of aromaticity owing to the
relative ease with which they can be computed. For that reason, they have been used extensively
in the study of aromaticity and antiaromaticity of the heteroles discussed previously in this
section.
18
NICS(3) –7.6
NICS(2) –10.2
NICS(1) –9.8
NICS(0) –8.0
Figure 1-12 NICS values for benzene. Calculations were performed at B3LYP/6-311+G(d) level
1.5 Thesis goals
This thesis will discuss the synthesis, characterization and reactivity of π-conjugated
organoboron compounds. With the remarkable properties of ladder, main group element-
containing π-systems and boroles in mind, Chapter two presents our findings into a
photochemical synthetic route to the first benzoborole-fused benzoborole derivative. One of the
issues to overcome in this endeavour was the air and moisture sensitivity of three-coordinate
boron compounds. Therefore, incorporation of bulkier substituents such as mesityl or
triisopropylphenyl was explored to provide enough steric stabilization for practical utility.
Chapter three discusses the redox chemistry of the boron-containing heterocycles prepared in
Charter two. Furthermore, it also discusses a thermal pathway to the synthesis of benzoborole-
fused benzoborole via a novel water catalyzed isomerization. The last chapter focuses on the
reactivity of the compounds presented in Chapter two and three towards several small molecules,
such as carbon monoxide and carbon dioxide.
19
Chapter Two: Towards the synthesis of benzoborole-fused benzoborole derivatives: The
photochemical route
2.1 Introduction
2.1.1 Previously reported benzoborole-fused benzoheteroles
With the desire of producing a highly polar structure by incorporation of a zwitterionic
bridging fragment, the Yamaguchi group published the synthesis of a series of benzoborate-fused
benzophosphonium derivatives in 2008.98 This paper was a seminal report in what would be a
growing field in the main group-containing π-electron systems.99 They key process in the
syntheses of such compounds was an intramolecular nucleophilic attack of the phosphanyl group
on the acetylene moiety, promoting a cascade cyclization (Scheme 2-1).100 The nucleophilicity of
the phosphanyl group played a crucial role in the cascade cyclization as shown by the lack of
cyclized product when chlorodiphenylphosphane was used. Even when the solution was refluxed
in 1,2-dichloroethane only trace amounts of the cyclized compound 2-I was observed. However,
the use of the more nucleophilic phosphanes chlorodicyclohexylphosphane and di-tert-
butylchlorophosphane resulted in the spontaneous formation of the moisture and air stable
cyclized products 2-II and 2-III at room temperature (Scheme 2-1). X-ray crystallographic
analysis on 2-II confirms the structure to be planar. Furthermore, the UV-Vis absorption
spectrum of compound 2-III has an absorption band with the maximum at 396 nm, attributed to
a charge transfer transition from the benzoborate function to the benzophosphonium moiety. In
the fluorescence spectrum, compound 2-III exhibits a yellow fluorescence with a maximum at
20
517 nm. The emission maximum of 2-III is about 160 nm longer than the bis-carbon-bridged
stilbene 1-II and 100 nm longer than the bis-silicon-bridged stilbene (benzosilole-fused
benzosilole) 1-VIIa discussed in Chapter one.25,101
R R
P
2-III (R=Cy)
2-II (R=t-Bu)
B
Mes Mes
Br Mes2B
1) n-BuLi 1) t-BuLi
2) Mes2BF 2) R2PCl
Br Br Mes2B
1,2-bis(2-bromophenyl)ethyne 2-I (R=Ph)
PPh2
R R
B R R
B
P
R P R R
R
Scheme 2-1 Formation of benzoborate-fused benzophosphonium derivatives98,102
The Yamaguchi group decided to further investigate this intramolecular cyclization
reaction by a systematic study in terms of the substituent effects.102 They found that more
electrophilic boryl groups also favour the cyclization, but the reactions required high
temperatures (60 ºC). Theoretical studies showed that the cyclization is indeed promoted by the
nucleophilic phosphanyl group, but the electrophilic boryl group also contributes to the lowering
of the activation energy. They also found computational evidence to suggest that the cyclization
is not a concerted process, but instead the phosphorus first approaches the acetylene moiety.102
21
As mentioned before, the benzoborate-fused benzophosphonium derivatives showed a
dramatic red-shifted absorption and emission spectra compared to the ladder benzoheterole-fused
benzoheterole derivatives discussed in Chapter one. However, the incorporation of a three-
coordinate boron center instead of a tetra-coordinate one seems more appealing because the
empty p-orbital can participate in the conjugation of π-electrons.5,7,8 Furthermore, theoretical
studies have suggested interesting and unusual electronic properties for borole-containing π-
conjugated systems.6,103 Until the work described in this chapter there were no reports of
benzoborole-fused benzoborole derivatives,104 but very recently Yamaguchi has reported the
synthesis and characterization of several benzoborole-fused benzoheterole derivatives.105 The
benzoborole-fused benzothiophene derivative 2-IV was prepared using 3-bromo-2,2-bithienyl-3-
boronic ester as the key precursor, and the 2,4,6-triisopropylphenyl (Tip) group was installed
using its Grignard reagent in THF (Scheme 2-2). Lithium-halogen exchange was performed
using t-BuLi, followed by quenching with sulfur powder. The generated anion subsequently
underwent an intramolecular nucleophilic attack to produce the desired compound 2-IV, with a
mechanism akin to the one reported for the synthesis of 2-I (Scheme 2-1). Despite the fact that a
lower antiaromatic character and higher stability was predicted for compound 2-IV based on the
electron donating capability of the thiophene unit, the thiophene-fused borole showed a
surprisingly high antiaromatic character and air and moisture sensitivity.105 The UV-Vis
absorption spectrum of compound 2-IV has an absorption band with the maximum at 469 nm,
which was attributed to a HOMO-LUMO transition by TD-DFT calculations. Unlike the
benzoborate-fused benzophosphonium derivatives, compound 2-IV is non-emissive.
22
O Tip
O B O B Tip
1) t-BuLi B
t-BuLi
THF 2) S8
S
Br Br
2-IV
Scheme 2-2 Synthesis benzoborole-fused benzothiophene 2-IV105
Yamaguchi et al. have also reported the synthesis of benzoborole-fused benzoheterole
derivatives containing nitrogen, oxygen and sulfur using a similar route as for the thiophene-
fused 2-IV (Scheme 2-3).24 All the compounds have nearly coplanar frameworks, except for
derivative 2-V, which slightly deviated from planarity with dihedral angles between the central
borole and two terminal benzene rings of 9.03(10)º and 6.59(12)º. However, this was attributed
to packing effects in the crystal structure of the material.24 Compounds 2-V, 2-VI, and 2-VII
showed nearly identical absorption spectra with broad absorption maxima at 479 nm, 468 nm,
and 474 nm respectively. As in compound 2-IV, the heterocycles enhance the antiaromatic
character of the borole fragment as shown by the increment in the NICS values. This is in
contrast to the observations made for the dibenzoborole derivative 1-IX, where the presence of
the benzene rings decreased the antiaromaticity of the systems.57
O
Mes
B O
1) MesMgBr B 2-V: E = NMe
B
2-VI: E = O
E
2) t-BuLi 2-VII: E = S Tip
E
1-IX
Br
Scheme 2-3 Synthesis of benzoborole-fused benzoheterole derivatives24
23
2.2 Synthetic strategies
In order to prepare the target benzoborole-fused benzoborole, we envisioned two synthetic
routes which are illustrated in Scheme 2-4. The first (A) is a boron-silicon exchange57,106,107 in
the benzosilole-fused benzosilole 1-VIIa reported by Yamaguchi,25 followed by addition of an
aryl magnesium compound, such as mesitylmagnesium bromide. The second one (B) is very
similar to the route used in the synthesis of benzosilole-fused benzosilole derivatives,25 and it
involves the addition of a strong reducing agent to a 1,2-bis(2-(chloro(aryl)boryl)phenyl)ethyne
derivative (2-3Ar) in order to promote a nucleophilic attack on the boron center. We first
attempted to prepare the desired benzoborole-fused benzoborole by treatment of compound 1-
VIIa with BBr3 (route A) because this route requires less steps and, the incorporation of bulky
substituents on the boron center, in order to protect the electrophilic center, was predicted to be
facile by simple addition of the lithiated or Grignard reagents. However, after allowing
derivative 1-VIIa to react with neat BBr3 at 100 °C for 48 hours, no clean transmetallation was
observed. Therefore we focused our attention on route B, which first required the synthesis of the
crucial precursors 1,2-bis(2-(chloro(aryl)boryl)phenyl)ethynes 2-3Ar.
24
Route A
Br Ar
Si BBr3 B ArMgBr B
- SiMe2Br2 - MgBr2
Si B B
Br Ar
1-VIIa
Route B Ar
Ar Ar
Cl B Cl
B
B
2 e–
- 2 Cl–
B
B Cl Ar
B
Ar Cl
2-3Ar Ar
Scheme 2-4 Feasible routes to prepare the target benzoborole-fused benzoborole derivative
2.3 Synthesis of 1,2-bis(2-(chloro(aryl)boryl)phenyl)ethyne precursors
We first tried to prepare the 1,2-bis(2-(chloro(phenyl)boryl)phenyl)ethyne derivative 2-3Ph
by direct quenching of the lithiated 1,2-bis(2-bromophenyl)ethyne27 with dichlorophenylborane,
but this only led to a mixture of intractable products (route A, Scheme 2-5). Therefore, we
decided to take advantage of the facile B/Sn transmetallation81,82,84,108 by making 1,2-bis(2-
(trimethylstannyl)phenyl)ethyne 2-1 as the key compound to generate the targeted boranes. First,
1,2-bis(2-bromophenyl)ethyne27 was lithiated at low temperature with t-BuLi then quenched
with Me3SnCl. Compound 2-1 was isolated as an off-white solid in 83% yield. As expected, in
the 1H NMR and 13C NMR spectra of compound 2-1 it is possible to observe coupling to the low
abundance, NMR active nuclei of tin via satellite peaks. The methyl groups show coupling
constants of 2J117SnH = 27 Hz and 2J119SnH = 28 Hz in the 1H NMR spectrum. The aromatic
protons also show coupling to tin, but it is more difficult to determine the coupling constant
25
values because the four aromatic protons appear as two multiplets, one centered at 7.51 ppm and
the other one at 7.32 ppm. In the 13C NMR spectrum, the methyl groups show coupling constants
of J117SnC = 170.8 Hz and J119SnC = 178.8 Hz. Likewise some of the aromatic carbons also show
119/117
coupling to tin; however, the Sn coupling is unresolved. Compound 2-1 was initially
isolated as an oil after column chromatography, but after a couple of hours sitting at room
temperature the compound slowly solidified.
Route A 1) 4 t-BuLi
X
2) 2 PhBCl2
Br Route B Me3Sn
1) 4 t-BuLi
2) 2 SnClMe3
Br SnMe3
2-1, 83%
BCl3 PhBCl2
Ph
Ar Cl Cl B
Cl B Cl B
CuAr
B Cl
B Cl B Cl Ph
Ar Cl
2-2, 85% 2-3Ph, 55%
2-3Mes: Ar = 2,3,6-trimethylphenyl, 84%
2-3Tip : Ar = 2,3,6-triisopropylphenyl, 70%
Scheme 2-5 Synthetic route to prepare compounds 2-3Ar
Boron-tin transmetallation is relatively facile with less sterically demanding
dichloroarylboranes.109 Hence, compound 2-3Ph was synthesized by direct transmetallation of
1,2-bis(2-(trimethylstannyl)phenyl)ethyne 2-1 with commercially available
dichlorophenylborane in 55% yield at room temperature; however, when the same strategy was
26
used with dichloromesitylborane,110,111 no product was observed even at 110 ºC overnight.
Isolation of more sterically encumbered 1,2-bis(2-(chloro(aryl)boryl)phenyl)ethynes was
achieved via 1,2-bis(2-(dichloroboryl)phenyl)ethyne 2-2 which was synthesized as an orange
solid in 85% yield by treating organotin compound 2-1 with an excess of BCl3. Even though our
group has used BCl3 gas in the past when performing the B/Sn exchange,74,80 during the
development of this thesis a commercially available 1 M solution in hexanes or heptane was

11
preferred because it was easier to add the desired amount of BCl3. The B NMR resonance of
compound 2-2 appears at 55.5 ppm, well in agreement with dichlorophenylborane (55.6 ppm).112
Incorporation of the bulkier aryl rings 2,4,6-trimethylphenyl (Mes) and 2,4,6-triisopropylphenyl
(Tip) was accomplished by transmetallation of one chloro substituent per boron with mesityl
copper (I)113 or 2,4,6-triisopropylphenyl copper (I)114 following the procedures reported by
Manners and Jäkle in the synthesis of 2,4,6-trimethylphenyldichloroborane.110,115 The
corresponding starting materials were stirred at 65 ºC and after a couple of minutes formation a
white suspension was observed, which was assumed to be CuCl. The solution was stirred at this
temperature for 16 h, the time required to drive the reaction to completion as determined by 1H
NMR spectroscopy. Compound 2-3Mes was isolated as a pale yellow solid in 84% yield and
compound 2-3Tip as a colorless solid in 70% yield. Solids 2-3Mes and 2-3Tip are moisture sensitive
11
compounds whose B NMR spectra exhibit signals at 68.4 and 66.3 ppm, respectively,
characteristic of chlorodiarylborane compounds115-117 and significantly downfield shifted
compared to the stating material 2-2 (55.5 ppm).
Apart from NMR spectroscopy and high-resolution mass spectroscopy compound 2-3Tip
was also characterized by X-ray diffraction (Figure 2-1) and all the parameters are in agreement
with the expected structure. The C1-C1’ bond distance is 1.199(3) Å, which is characteristic for a
27
carbon-carbon triple bond.118 Even though most diarylacetylenes do not have an ideal 180º angle
around the acetylene carbon,119-122 the deviation only accounts for a few degrees. However, the
C2-C1-C1’ angle in 2-3Tip measures 169.2(2)º, which is significantly more pronounced than in
related compounds. Likewise, the angles around the boron center are different than 120º; the
biggest difference being the C3-B-C8 angle of 130.9(2)º. Most likely these deviations are
attributable to the steric demand of the molecule and a repulsive interaction between the phenyl
Tip ring and the hydrogen attached to C7. The distance between C7-H and the phenyl Tip ring is
2.509 Å and the C7-H bond distance is slightly shorter compared to all the C-H bond distances -
and the average- in the same aryl ring (0.92(3) Å vs an average of 0.95(3) Å). Such interaction
pushes the aryl ring outward relative to the alkyne, deviating the alkyne angle from the ideal 180º
and making the angles around the boron center fairly different from the idealized angle of 120˚.
This interaction can also be seen in the 1H NMR spectrum, where the hydrogen attached to C7
appears at 6.98 ppm as a broad resonance located at the highest field of all the aromatic
resonances. One might anticipate that the C7-H would experience a paratropic ring current and
thus appear downfield. This is not the case because in solution most likely the phenyl group
exchanges position with the chorine atom by rotation around the boron center. Therefore, only an
average of both conformations is observed.
28
atoms have been removed for clarity
Table 2-1 Selected Metrical Data for 2-3Tip
Bond Distances (Å) Bond Distances (Å)

C3-B 1.547(3) C6-C7 1.373(4)
C1-C1’ 1.199(3) C7-C2 1.391(3)
C8-B 1.553(3)
C2-C1 1.427(3) Bond Angles (º)
C2-C3 1.417(3) C2-C1-C1’ 169.2(2)
C3-C4 1.399(3) C3-B-C8 130.9(2)
C4-C5 1.370(3) C8-B-Cl 113.3(3)
C5-C6 1.378(4) C3-B-Cl 115.7(2)
29
2.4 Reduction of 1,2-bis(2-(chloro(aryl)boryl)phenyl)ethynes. Synthesis of
dibenzodiboracyclobutylidenes
With the key starting materials in hand, reduction using strong reducing agents was
attempted. Potassium graphite (KC8)48,123-126 was chosen as the reducing agent since its reduction
potential is very negative and the by-product graphite is completely inert and facile to remove by
filtration.127 Furthermore, KC8 is an easily handled powder, which makes it convenient to use in
small test scale reactions. When 2-3Ph was mixed with 2 equivalents of KC8, no product was
observed by NMR spectroscopy (the 1H NMR spectrum showed only a featureless broad
resonance in the aromatic region); however, when 4 equivalents of reductant were used, a
symmetric pattern appeared in both the 1H and 13C NMR spectra. That compound was believed
to be the over-reduced dianion 2-5Ph’ (Scheme 2-6); several oxidizing agents such as iodine25 and
1,2-dibromoethane128 were used in an attempt to generate the desired product, but this strategy
was unsuccessful. Furthermore, the over-reduced compound was difficult to handle due to the
low solubility in common organic solvents and the identity of the compound could not be
elucidated. It was presumed that more steric protection around the boron center was required to
stabilize the molecule and so the chemistry of the bulkier mesityl derivative 2-3Mes was explored.
Ar
Ar Ph
Cl B K
2 eq KC8, THF B B
?
- 2KCl B B
K
B Cl Ar Ph
Ar 2-5Ph'
2-3Ar 2-5Ar
Ar = Ph: Ar = phenyl Ar = Mes: Ar = 2,3,6-trimethylphenyl Ar = Tip: Ar = 2,3,6-triisopropylphenyl
Scheme 2-6 Reaction of compounds 2-3Ar with KC8
30
The mesityl derivative showed to be more conducive to the formation of a clean product.
As the standard procedure, 1 equivalent of 2-3Mes was mixed with 1.9 equivalents of KC8, using
THF as solvent. The reaction mixture was filtered, layered with hexanes and cooled to –35 °C
for 3 days. After this period of time, a solid was isolated as yellow flakes that showed strong
green fluorescence under UV light. 1H, 13C{1H} and 11B NMR spectra were consistent with the
desired product (Figure 2-2), but this compound was never isolated 100% pure. There was
always a green by-product along with the yellow solid. The signals for this by-product are
labeled with an asterisk in Figure 2-2. These reactions were carried out on a 50 mg scale and the
highest yield ever achieved was 9% (4 mg of product). We were unable to grow single crystals
suitable for X-ray diffraction in order to unequivocally confirm the identity of the yellow solid,
or the green impurity, and so while these observations were promising, the situation became
more clear when the analogous reductions were performed on 2-3Tip, incorporating the bulkier
2,4,6-triisopropylphenyl group.
When the more sterically protected compound 2-3Tip was reacted with KC8 using the
same protocol as described before, only a minimal amount of yellow product was isolated;
however, no impurities were observed in the 1H NMR spectrum of the crude sample. In an
attempt to use more gentle conditions, potassium naphthalenide (KNaph)127 was used as the
reducing agent. A freshly prepared solution of potassium naphthalenide was added drop-wise to
a THF solution of 2-3Tip at –78 °C. Immediately the solution changed from colourless to deep
purple. The resulting mixture was allowed to reach room temperature over the course of two
hours during which the solution slowly turned brownish yellow. After evaporation of the solvent
and removal of naphthalene by sublimation, a brownish yellow solid was left in the flask. This
solid was washed with hexanes, giving a bright yellow solid in 55% yield (Scheme 2-7). This
31
compound also displayed green fluorescence when irradiated under UV light in both solution and
solid state. Initially this compound was also presumed to be the desired benzoborole-fused
benzoborole 2-5Tip; nonetheless, X-ray crystallographic analysis surprisingly revealed the
structure to be the thermodynamically less favoured dibenzodiboracyclobutylidene 2-4Tip.
Ar Ha
Hb
B
?
11
B NMR Spectrum
He o-Me
Hc
67.00
B
Hd p-Me
o-Me o-Me
He He
p-Me
6.1
3.0
80 70 60 50
2.42 2.39 2.36
Hd Hb Hc
Ha
✶
✶ ✶ ✶
1.0
1.1
1.0
2.0
1.0
7.65 7.60 7.55 7.50 7.45 7.40 7.35 7.30 7.25 7.20 7.15 7.10 7.05 7.00 6.95 6.90 6.85 6.80 6.75
Figure 2-2. 1H and 11B NMR spectra of the product of the reaction between KC8 and 2-3Mes
(CD2Cl2, 400 MHz)
32
Tip
Cl B Tip
2 eq KNaph, THF B
Tip =
- 2KCl B
B Cl Tip
Tip 2-3Tip 2-4Tip, 55 %
Scheme 2-7 Synthesis of 2-4Tip
These results strongly suggest that the compound isolated in the reaction of 2-3Mes with
KC8 is the four-membered ring 2-4Mes, and not the benzoborole-fused benzoborole as was
assumed in the first place. Furthermore, this also demonstrates that the steric protection around
the boron center is detrimental in order to isolate and characterize the desired cyclized
compounds.
2.4.1 X-ray crystallography
As mentioned in the previous section, the X-ray crystallographic analysis of 2-4Tip
revealed the structure to be the dibenzodiboracyclobutylidene structural isomer (Figure 2-3).
Despite the fact that the data were collected at 123 K, the B-aryl group and the isopropyl groups
attached to it were disordered. However, the central part of the structure was free of any disorder
and the analysis unequivocally establishes the connectivity of the molecular structure of 2-4Tip.
33
Table 2-2 Selected bond distances (Å) and angles (°) for 2-4Tip
Bond Distances (Å) Bond Angles (º)

C1-B1 1.576(5) C1-B1-C7 86.6(3)
C7-B1 1.580(5) C1-B1-C8 138.3(3)
C7-C6 1.485(5) C7-B1-C8 134.2(3)
C6-C5 1.386(5) C1-C6-C7 96.4(3)
C5-C4 1.381(5)
C4-C3 1.388(6)
C3-C2 1.371(7) Dihedral Angles (º)
C2-C1 1.384(5) C13-C8-B1-C7 67.6(6)
C1-C6 1.416(5) C1-C6-C7-C7’ 179.7(2)
C7-C7’ 1.330(5)
34
The X-ray structure of 2-4Tip revealed some interesting features. The dihedral angle C1-
C6-C7-C7’ is 179.7(2)° and the sum of the angles around boron is 359.1°, suggesting a coplanar
structure. The Tip groups are not arranged perpendicularly, instead they are canted relative to the
B2C6 plane with a dihedral angle C13-C8-B1-C7 of 67.6(6)°. The trigonal planar geometry about
the boron centers is significantly distorted due to the necessarily small C1-B1-C7 angle of
86.6(3)°. The two boracycles are linked by a C-C double bond (1.330(7) Å),118 and the boron
atoms are found in a trans arrangement about this double bond. All carbon atoms are sp2-
hybridized, which causes a planar structure and allows conjugation throughout the whole 14 π-
electron system. Organoboron compounds with a boracyclobutene moiety are extremely
scarce129-132 and the strain associated with the core four-membered rings likely contribute to the
moisture sensitivity of the compounds, despite the considerable steric protection of the Lewis
acidic boron. The steric bulk imparted by the Tip groups of 2-4Tip precluded the formation of
extended tight π-stacking motifs in the solid-state, however close C–C edge-to-face (3.553(5)
Å)84 contacts were present between the arene rings of the main framework and the Tip aryl rings
of adjacent molecules (Figure 2-4).
35
Figure 2-4 Thermal ellipsoids (50%) diagram showing packing motif in 2-4Tip
2.4.2 Nuclear Magnetic Resonance (NMR) Spectroscopic Analysis
In solution compound 2-4Tip displays C2h symmetry. Since there is a C2 axis along the
carbon-carbon double bond and a σh plane, there are only 5 resonances for the aromatic protons,
4 belonging to the main framework and one to the perpendicular aromatic ring (Figure 2-5). The
1
H NMR spectrum shows the characteristic septet resonances for the isopropyl methine groups
overlapping at 2.98 and 2.92 ppm. The isopropyl methyl groups located in the ortho position
appear as a broad singlet at 1.18 ppm due to the overlap of the signals.
36
Tip
B
Figure 2-5 1H NMR spectrum of 2-4Tip (CD2Cl2, 600 MHz, 293 K)
13
The C{1H} NMR spectrum is also indicative of a C2h symmetric structure, although
only 2 out of 3 carbons attached to boron were observable in the 13C spectrum due to the large
13 11
quadrupolar moment of the boron center. The C nucleus is coupled to the B nucleus, and
thereby indirectly undergoes more rapid spin-lattice relaxation resulting in a broadened
resonance signal.116 Interestingly, those 2 carbons not only were assigned by 1

H-13C
Heteronuclear Multiple-Bond Correlation (HMBC) spectroscopy, but they were also observed in
the 13C{1H} NMR spectrum as broad small peaks at 156.4 and 147.1 ppm (Figure 2-6). Using 2D
spectroscopic analysis it was determined that the missing resonance belongs to the olefinic
37
carbon. Triarylboranes have 11B chemical shifts around 80 ppm,133,134 but when the boron center
is inserted into a π-system the chemical shifts move to higher field.135-137 The 11B NMR spectrum
of 2-4Tip shows a broad resonance at 70.1 ppm (in CD2Cl2), well in agreement with a three-
coordinate boron center inserted in a π-system74,80 and slightly downfield shifted compared to the
stating material 2-3Tip (66.3 ppm).
9 6 Tip
7
11 14 B
8 13 ? 1
B
12
2 4 10
11 4
5 5
12
3
1
11 3
9 7 6
8
12 2
14
13 10
Figure 2-6 13C{1H} NMR spectrum of 2-4Tip (CD2Cl2, 150 MHz, 293 K)
38
2.5 Photochemical Isomerization. Synthesis of the first benzoborole-fused benzoborole
derivative
Since 2-4Tip is a structural isomer of the desired benzoborole-fused benzoborole 2-5Tip,
and DFT computations (vide infra) suggest that it is significantly higher in energy than the fused
diborole, attempts to induce thermal isomerization were made, but no change in the 1H NMR
spectrum was observed after heating a toluene solution of 2-4Tip at 80 °C for 1 hour. Since the
photoisomerization of alkenes using UV light is a well known process,138,139 the photochemistry
of the compound was subsequently studied.
The electronic spectrum of compound 2-4Tip was investigated in diluted and oxygen free
solutions. In CH2Cl2, the boracycle 2-4Tip is yellow and displays a strong green fluorescence
emission ranging from 470-700 nm. The UV-Vis absorption spectrum (Figure 2-7) revealed a
moderate absorption band at 459 nm (ε = 7873 M−1 cm−1), a weak absorption peak at 370 nm (ε
= 6492 M−1 cm−1) and two intense absorptions at 314 nm (ε = 16664 M-1 cm-1) and at 262 nm (ε
= 24664 M-1 cm-1). In a quartz NMR tube (CD2Cl2, 0.016 mol/mL), the sample was irradiated at
460 nm for several hours, but even after 4 hours of irradiation, only minor new signals were
observed, which did not grow with time. However, when the sample was irradiated at 254 nm,
the formation of a new compound could be monitored by 1H NMR spectroscopy (Figure 2-8).
After 10 hours of irradiation there was clean formation of a new compound, which is also
evidenced by the change in the colour of the solution from yellow to dark green (see Figure 2-8
right). During the photoreaction the appearance and subsequent disappearance of another
compound was observed (peaks labeled with an asterisk in Figure 2-8). We were not able to
39
determine the identity of this intermediate species, but X-ray diffraction confirmed the final
product to be the desired benzoborole-fused benzoborole 2-5Tip (vide infra).
Figure 2-7 UV-Vis (top) and fluorescence (bottom) spectra of 2-4Tip measured in CH2Cl2 (10-4
M)
40
0 min
a
30 min
✶
✶ ✶ ✶
120 min
240 min
b
360 min
600 min
c
7.9 7.8 7.7 7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7 6.6 6.5 6.4
Figure 2-8 Photochemical reaction of 2-4Tip monitored by 1H NMR spectroscopy (irradiated in a

quartz NMR tube at 254 nm). The top spectrum corresponds to the 1H NMR spectrum of 2-4Tip
prior to irradiation; the middle traces are the spectra at partial conversion, with the peaks marked
by the * due to the intermediate; the bottom is the spectrum after full conversion to 2-5Tip. a =
solution of 2-4Tip; b = solution of 2-4Tip under UV light (254 nm); c = solution of 2-5Tip
The scale of the reaction was increased using a quartz cuvette. After 12 hours of
irradiation and solvent removal, the green solid was suspended in a minimal amount of hexanes
at –30 °C and filtered. The product was isolated in 50% yield and fully characterized by NMR
and high resolution mass spectrometry (Scheme 2-8). The NMR spectra suggested a symmetric
structure, with the same number of protons as in 2-4Tip (Figure 2-8).
41
Tip
Cl B Tip Tip
2 KNaph B B
hν
- 2KCl Tip =
B CH2Cl2
B
B Cl Tip
Tip
Tip
2-3Tip 2-4Tip , 55% 2-5Tip, 50%
Scheme 2-8 Synthesis of benzoborole-fused benzoborole 2-5Tip
In 1978 Willner reported the in-situ generation of a dibenzopentalene dication upon
treatment of 1,9-dimethyldibenzo[b,f]pentalene with SbF5 in SO2ClF at –78 ºC (Scheme 2-9).140
Interestingly, the two-electron oxidation product 1,9-dimethyldibenzo[b,f]pentalenedication was
obtained as a dark green solution, same colour than the isoelectronic 2-5Tip. Even though the
compound was not characterized by X-ray diffraction, evidence of its formation came from
NMR spectroscopy. The 1H NMR spectrum of the resulting solution showed considerable
downfield resonances compared with those of the starting material, which was attributed to the
electronic change in the π-system and the formation of a diamagnetic ring current. Similar shifts
in the resonances were also observed in the 13C NMR spectrum.140,141
Me Me
SbF5
Me Me
Scheme 2-9 Synthesis of 1,9-dimethyldibenzo[b,f]pentalene dication140
42
2.5.1 X-ray crystallography
The boron centres in 2-5Tip adopt a distorted trigonal planar geometry with a C3-B1-C1
angle of 102.1(2)°. The benzoborole skeleton in 2-5Tip is completely planar, which can be
appreciated with the dihedral angles C1-C1’-C2-C3, C1’-C1-B1-C3 and C1-C1’-C2-C7, equal to
0.1(4)°, 0.4(2)°, and 179.6(3)° respectively. Unlike 2-4Tip, the Tip groups are essentially
perpendicular relative to the B2C6 plane with a dihedral angle C1-B1-C8-C13 of –90.1(4)°. The
bond lengths of the borole ring in 2-5Tip differ only slightly compared to benzoborole-fused
benzoheterole reported by Yamaguchi and co-workers.24,105 Notably, there is a large bond
alternation in the butadiene moiety. The C1-C1’ and C2-C3 bond lengths are 1.367(5) and
1.419(13) Å respectively, while the C1’-C2 bond length is 1.480(4) Å.
atoms have been removed for clarity.
43
Table 2-3 Selected bond distances (Å) and angles (°) for 2-5Tip

C1-B1 1.571(4) C1-B1-C3 102.1(2)
C3-B1 1.588(4) C1-B1-C8 128.6(2)
C1’-C2 1.480(4) C3-B1-C8 129.2(2)
C2-C7 1.380(4) C3-C2-C1’ 110.2(2)
C7-C6 1.401(4)
C6-C5 1.371(3)
C4-C3 1.373(4) C1-B1-C8-C13 –90.1(4)
C3-C2 1.419(3) C1-C1’-C2-C3 0.1(4)
C1-C1’ 1.367(5)
Similarly to compound 2-4Tip, the steric bulk imparted by the Tip groups of 2-5Tip
prohibited the formation of π-stacking motifs in the solid-state. Intermolecular interactions
similar to the ones observed in 2-4Tip were also precluded due to the co-crystallization of solvent
molecules (dichloromethane) in the unit cell.
2.5.2 Nuclear Magnetic Resonance (NMR) Spectroscopy Analysis
As the starting material 2-4Tip, compound 2-5Tip also displays C2h symmetry in solution.
Therefore only five resonances for the aromatic protons are present in the 1H NMR spectrum
(Figure 2-10); four belonging to the benzene ring fused to the borole unit and the other one to the
Tip group. Unlike compound 2-4Tip, the septet resonances for the isopropyl methine groups do
44
not overlap at all and they are clearly seen at 2.96 and 2.69 ppm. The chemical shift of the
isopropyl methine protons located above and below the boron center (2.69 ppm) is very similar
to the chemical shift in the benzoborole-fused benzothiophene 2-IV (2.66 ppm) reported by
Yamaguchi,24 but both resonances are significantly different compared to dibenzoborole 1-IX
(2.52 ppm) (Figure 2-11). This shows that the exchange of the benzene for a heterole ring
changes the electronic properties of the borole unit.
All the expected resonances are observed in the 13C{1H} NMR spectrum of boracycle 2-
5Tip, and the carbons attached to boron also appear as broad small signals at 176.2, 144.2 and
135.7 ppm (Figure 2-12). All the aromatic resonances appear in the expected region except for
the olefinic bridgehead carbon, whose resonance appears significantly downfield shifted at
11
176.16 ppm. The B NMR spectrum shows a broad resonance at 68.6 ppm (in CD2Cl2) which
was not significantly different from that observed for the stating material 2-4Tip (70.1 ppm).
45
Tip
B
Figure 2-10 1H NMR spectrum of 2-5Tip (CD2Cl2, 600 MHz, 293 K)
Tip
B S
B H H B H
H B H H 2.66 ppm
2.50 ppm 2.69 ppm
2-5Tip 2-IV
1-IX
Figure 2-11 Chemical shift of isopropyl methine protons
46
Tip
9 7 B 1
15 16 2
8 3
10 12
B
5
5 11
6 1 14
2
6
13
4
3
14 4
8 7
10 9
15 13
16 12 11
Figure 2-12 13C{1H} NMR spectrum of 2-5Tip (CD2Cl2, 600 MHz, 293 K)
2.5.3 Absorption Spectroscopy
The electronic spectra of compound 2-5Tip was investigated in diluted and oxygen free
solutions. In CH2Cl2, the borocycle 2-5Tip is dark green and has a very strong absorption at 287
nm (ε = 94984 M−1 cm−1), a weak absorption from approximately 320 nm to 500 nm (ε380 =
~5583 M−1 cm−1) and a very weak broad absorption band in the 530 to 740 nm range (ε670 = 591
M−1 cm−1). This last absorption band is attributable to the HOMO-LUMO transition and it is π à
π* in character (Figure 2-13). Unlike compound 2-4Tip, compound 2-5Tip does not show
47
fluorescence emission under UV light and most likely this is because the HOMO-LUMO
transition is forbidden.
Figure 2-13 UV-Vis absorption spectrum of 2-5Tip measured in CH2Cl2 (10-4 M)
2.5.4 Aromaticity and antiaromaticity. Nucleus Independent Chemical Shift (NICS)

Calculations
Compounds 2-4Tip and 2-5Tip have 14 π-electrons and 2-5Tip may be expected to exhibit
Hückel aromaticity; however, the borole rings at its core are classical examples of antiaromatic
rings.142,143 To probe the aromatic/antiaromatic character of the π-framework in 2-5Tip, we
carried out NICS85,97 calculations at the B3LYP/6-311+G(d)144 level of theory. These
calculations, introduced by Schleyer in 1996,97 allow the computation of absolute magnetic
shielding at the centre of a ring and at various distances (increments of 1 Å) above and below the
centre of the ring. “Dummy atoms” are placed in these positions and then nucleus independent
48
chemical shifts are calculated. Conventionally, magnetic shielding is measured in the plane of
the aromatic ring, denoted NICS(0), and 1 Å above the plane of the ring, denoted NICS(1). A
negative NICS value implies the ring is aromatic, for example, benzene has a reported NICS(0)
value of –9.7 at the B3LYP/6-31G+(d) level.85 Correspondingly, a positive NICS value implies
the ring is antiaromatic.145
The NICS values for the five-membered rings (Table 2-4) are indicative of antiaromaticity
and the flanking benzene rings are less aromatic than benzene itself (NICS(0) = –9.785). Thus, in
this system, which by the Hückel convention is aromatic as a whole, the annulated aromatic
benzene rings stabilize its antiaromatic core.
Table 2-4 NICS (1/0) and NICS(1)zz values for 2-5Tip
Tip
B
a
b
B
Tip
Ring NICS(0) NICS(1) NICS(1)zz‡146

a –3.2 –6.2 –11.8
b 14.9 6.3 21.8
‡
NICS(n)zz refers to the total MO contribution to the zz component of the NICS tensor. The “z” direction is
perpendicular to the ring. In this chapter the NICS(1)zz were included in order to compare with the literature values
reported by Yamaguchi (Iida, A.; Sekioka, A.; Yamaguchi, S. Chem. Sci. 2012, 3, 1461).
49
Compound 2-5Tip has a less positive NICS(1)zz value than the dibenzoborole 1-IX and the
heterole-fused benzoboroles 2-IV - 2-VII (Table 2-5), suggesting that compound 2-5Tip is less
antiaromatic. Interestingly, this behaviour is the opposite of that observed in the other heterole-
fused benzoboroles, where the presence of the other heteroatoms increased the antiaromaticity.
Despite the fact that there is no linear relation between the antiaromaticity of the borole fragment
and the aromaticity of the fused-heteroacene it can be observed that the antiaromaticity of the
benzoborole increases when is fused to a more aromatic heteroacene.24 The NICS values for
benzene, furan, thiophene, and pyrrole are –9.7, –12.3, –13.6, –15.1 respectively.97 Of course,
the lowest antiaromatic borole is obtained when the fragment is fused to another borole ring
(compound 2-5Tip).
Table 2-5. Borole NICS(1)zz values for compounds 2-VII – 2-VIII and 2-5Tip
Tip Cmpd NICS(1)zz Ar

B B
2-IV 30.1
1-IX
2-V 31.7 E
2-IV: Ar = Tip, E = S
2-VI 27.6 2-V: Ar = Mes, E = NMe
2-VI: Ar = Mes, E= O
2-VII 30.4 2-VII: Ar = Mes, E = S
1-IX 24.5
Tip
2-5 21.8
Even though compound 2-4Tip cannot be actually classified as an aromatic or antiaromatic
system because the rings are separated by the central double bond (therefore, could not be
considered a cyclic system) NICS calculations were performed on the individual rings to
50
evaluate their aromatic/antiaromatic character. Furthermore, due to the presence of the p-orbitals
in the adjacent double bonds and at the boron centers conjugation is possible throughout the
entire dibenzodiboracyclobutylidene system (see HOMO in Figure 2-15). For compound 2-4Tip
characteristic NICS values (Table 2-6) suggest a somewhat antiaromatic character of the
boracyclobutylidene framework. Additionally, the varying bond lengths in these four-membered
rings might be regarded as another aspect of antiaromaticity. Certainly, the fused aromatic rings
strongly stabilize the system in 2-4Tip (NICS(0) = –5.0, NICS(1) = –7.8).
Table 2-6 NICS (0/1) and NICS(1)zz values for 2-4Tip
Tip
a B
b
B
Tip
Ring NICS(0) NICS(1) NICS(1)zz146

a –5.0 –7.8 –13.8
b 13.1 0.6 8.7
2.5.5 Electrochemical Studies
Cyclic voltammetry experiments were performed in THF using Bu4NPF6 as the
supporting electrolyte; the potentials were referenced against the ferrocene/ferrocenium ion
51
couple. Compounds 2-4Tip and 2-5Tip are both reduced by one and two electrons in sequential
one-electron processes (Figure 2-14). Compound 2-4Tip exhibits irreversible reduction waves; the
first reduction potential was observed at –2.47 V and the second at –2.89 V. Conversely, ladder
diborole 2-5Tip shows a reversible reduction wave at –1.51 V followed by a second, irreversible,
reduction wave at –2.42 V. The reversible wave was only observed when the scanning window
was shortened during the measurement (scan frame: –1.75 – 0.3 V). Based on control
experiments using potassium salts of the radical anions and dianions (vide infra), the
irreversibility of these reduction waves is likely due to the reactivity of the reduction products
with the supporting electrolyte. Both reduction potentials of 2-5Tip are considerably less negative
than the ones observed for heterole-fused benzoboroles 2-IV – 2-VII (E1/2 = –1.89 V to –2.25 V
for the first reduction potential and Epc = –2.78 V to –3.04 V for the second reduction
potential).24
Figure 2-14 Left: cyclic voltammetry traces for 2-4Tip. Right: cyclic voltammetry traces for 2-
5Tip (insert corresponds to the reversible wave when potential does not exceed –1.75 V). Cyclic
voltammetry was carried out at a scan rate of 100 mV/s in THF with 1mM substrate and 0.1M
[NBu4][PF6] as the supporting electrolyte. Ferrocene was added as an internal standard.
52
2.6 Proposed Mechanism of Photoisomerization
The mechanism of the clean photoconversion of 2-4Tip to 2-5Tip is not known with
precision, but the visible spectra and TD-DFT calculations provide valuable insight into its
character.§ Compound 2-4Tip exhibits major absorptions at 263 nm (ε = 24664 M−1 cm−1) and
314 nm (ε = 16664 M−1 cm−1), a weak absorption peak at 370 nm (ε = 6492 M−1 cm−1) and a
moderate absorption band at 459 nm (ε = 7873 M−1 cm−1); notably, selective irradiation of the
lower energy absorptions does not result in any conversion of 2-4Tip to 2-5Tip. Thus, it is the
excitation at 263 nm that results in productive photoreaction.
LUMO LUMO+2
Tip
B
Tip
263 nm HOMO
HOMO-6
(286 calc)
f = 0.217
Figure 2-15 Molecular orbitals relevant for the photoreaction: HOMO-6, HOMO, LUMO,
LUMO+2 (isocontour value 0.02), oscillator strength, and wavelength
§
Dr. Benedikt Neue performed these calculations during his postdoctoral fellowship in the Piers group.
53
TD-DFT calculations (B3LYP/6-31G(d), td=(states=20)) on 2-4Tip reproduce the
experimental absorption spectrum quite accurately and show that the absorptions are π à π* in
character. The lower energy transitions are mainly comprised of the HOMO to LUMO transition;
both orbitals have large contributions from the π-orbitals associated with the central C=C double
bond. However, the band at 263 nm (calc.: 286 nm, f = 0.2168) corresponds mainly to π à π*
transitions with contributions from HOMO-6 to LUMO, but also HOMO to LUMO+2 (Figure
2-15). As can be seen, both of these populate antibonding π-orbitals associated with the B-C
bonds of the boracyclobutylidene rings, suggesting that photoinduced homolytic bond cleavage
is the key step in the isomerization of 2-4Tip to 2-5Tip.147
Scheme 2-10 summarizes a proposed mechanism and suggestions for the nature of the
observed transient intermediate in the reaction; the numbers in square brackets are the calculated
energies of the species in kcal mol-1. Not including the B-CAr bond, there are two B-C bonds
associated with the strained four-membered boracyclic rings in 2-4Tip, labelled a and b in
Scheme 2-10. Cleavage of bond a allows for direct formation of 2-5Tip, the formation of the two
five-membered rings in 2-5Tip is aided by the presence of a C=C double rather than triple bond.
Cleavage of bond b not only helps to explain the isomerization, but also allows for reasonable
speculation as to the nature of the minor intermediate observed in the reaction (Figure 2-8). The
photoproduct of cleavage of bond b can reform 2-4Tip, or form a B-B bond to give 2-VIII as
depicted in Scheme 2-10. Although such a diboracyclooctyne ring would be expected to suffer
from some strain, its computed energy is actually slightly less than that found for 2-4Tip.
Furthermore, a disilicon analogue has been reported to undergo photoconversion to the
benzosilole-fused benzosilole 1-VIIa,99,148 so it would be expected that 2-VIII would eventually
convert to 2-5Tip as the intermediate does. Another viable possibility for the identity of this
54
intermediate is the cis isomer of 2-4Tip, 2-IX in Scheme 2-10. Photoisomerization of alkenes is
well known138 and the energy of 2-IX is only 7 kcal mol-1 higher than that of the isolated trans
isomer.** Both of these structures are consistent with the observed symmetry of the compound on
the basis of its 1H NMR spectrum and both would be expected to fully convert to 2-4Tip upon
further irradiation, since the benzoborole-fused benzoborole isomer is substantially more stable
than all three compounds (2-4Tip, 2-VIII or 2-IX).
Ar Ar
hν B Ar
B B
254 nm
a B a
Ar B B
b
Ar Tip [-42.2]
Ar 2-5
2-4Tip [0.0]
hν
b
254 nm
Ar
B Ar Ar
hν
B B
B B
Ar Ar
B 2-IX [7.0]
Ar 2-VIII [-1.6]
Scheme 2-10 Proposed mechanism for the formation of 2-5Tip; path a involves photocleavage of
B-C bond a, path b, bond b. Numbers in square brackets indicate the energies (kcal mol-1) of the
species shown relative to 2-4Tip (SCS-MP2/6-311+G(d,p)//B3LYP/6-31G(d)+ZPE149).
**
Interestingly, addition of carbon dioxide to 2-4Tip produces the same intermediate observed in the photochemical
isomerization (this will be discussed in Chapter four). This suggests that the intermediate in the photochemical
isomerization is the cis isomer 2-IX, and that this species is not actually an intermediate in the isomerization, but a
product of a side reaction (cis-trans isomerization).
55
2.7 Summary and Conclusions
This chapter described the synthesis of the hitherto unknown benzoborole-fused
benzoborole 2-5Tip, which was prepared from the unexpected boracyclobutylidene 2-4Tip by a
light-driven isomerization. Both compounds represent new classes of boron-containing
heterocyclic frameworks, which were fully characterized. The NICS calculations showed that the
borole ring in compound 2-5Tip is less antiaromatic than the borole ring in other benzoborole-
fused benzoheterole derivatives, which is in agreement with Yamaguchi’s observations.
Furthermore, electrochemical studies showed that it’s possible to reduce both compounds and
this chemistry will be explored in the next chapter.
56
Chapter Three: Brønsted acid-catalyzed skeletal rearrangements in polycyclic conjugated
boracycles: a thermal route to benzoborole-fused benzoboroles
3.1 Introduction
The previous chapter described the synthesis and characterization of the first benzoborole-
fused benzoborole reported to date.104 Compound 2-5Tip was prepared by a light-driven
photoisomerization of 2-4Tip, which is the kinetic product in the reduction of the 1,2-bis(2-
(chloro(2,4,6-triisopropylphenyl)boryl)phenyl)ethyne precursor 2-3Tip.104 While small quantities
of pure 2-5Tip can be obtained in this way, attempts to garner workable amounts of 2-5Tip on a
preparative scale using this procedure were hampered by low efficiency. Most likely, the product
2-5Tip decomposes during the photoisomerization because of the prolonged irradiation required
to drive the reaction to completion. Therefore, we focused our attention on the discovery of a
thermal pathway for the isomerization of 2-4Tip to 2-5Tip.
3.1.1 Isomerization of the carbon analogue
It has been reported that the carbon analogue of compound 2-4Tip ((1,1’-
bi(benzocyclobutylidene), 3-I) undergoes a fast rearrangement in acetic anhydride containing
sulfuric acid to 5,10-dihydroindeno[2,1-a]indene, 3-II.150 The reaction was reported to proceed
by a sequence of 1,2-carbenium ion shifts as illustrated in Scheme 3-1.
57
H
H H
+
+
(CH3CO)2O, H2SO4
3-I 3-II
Scheme 3-1 Proton catalysed isomerization of 1,1’-bis(benzocyclobutylidene) (3-I)150
Accordingly, we attempted to catalyze the analogous isomerization of compound 2-4Tip
using weaker acids (both Brønsted and Lewis), but to no avail. In fact, when water was added to
2-4Tip, preferential ring opening of the boracycle took place, forming (E)-1,2-bis(hydroxy(2,4,6-
triisopropyl)boryl)-diphenylethene (3-1Tip) as shown in Scheme 3-2. The nature of this borinic
acid was supported by NMR spectroscopy and confirmed by X-ray crystallography (Figure 3-1).
Given the propensity of B-C bonds to undergo protic cleavage, this outcome is perhaps not too
surprising.137,151,152
Tip
Tip
B OH
B H2O
Tip =
B
HO B
Tip
Tip
2-4Tip 3-1Tip
Scheme 3-2 Formation of 3-1Tip
58

C3-B1 1.579(4) C3-B1-C1 114.5(2)
B1-C1 1.605(4) C1-B1-Ol 121.5(2)
C1-C1’ 1.363(4) C1-B1-C3 123.9(2)
B1-O1 1.353(4) B1-C1-C2 115.4(2)
C1-C2 1.500(4) C2-C1-C1’ 119.5(2)
B1-C1-C1’ 125.1(2)
Since compound 2-4Tip is electron deficient relative to the all-carbon analogue 3-I, we
postulated that its dianion, denoted as species a in Scheme 3-3 and formed by 2 electron
reduction of 2-4Tip, might undergo an acid catalyzed isomerization as observed for the all-carbon
59
system; subsequent oxidation of species b could be an alternative way to prepare compound 2-
5Tip (Scheme 3-3). In this chapter, the synthesis and characterization of di(benzo-
bis(borata)cyclobutylidene) (a) and dibenzo-bis(borata)pentalene (b) species along with their
reactivity towards Brønsted acids will be studied and discussed.
Tip
Tip Tip
B
2 e– B B
B B
B
Tip Tip
Tip
2-4Tip a
H+
Tip
Tip
B
B
B - 2 e– B
Tip Tip
2-5Tip b
Scheme 3-3 Proposed thermal pathway for the synthesis of 2-5Tip
3.2 Chemical reduction of compounds 2-4Tip and 2-5Tip
The viability of compounds 2-4Tip and 2-5Tip to undergo electrochemical reductions was
explored at the end of Chapter two and Table 3-2 shows a summary of the electrochemical data
previously discussed. The electrochemical studies displayed two sequential one-electron
processes, suggesting that it is possible to reduce both compounds by one and/or two electrons.
However, powerful reducing agents, such as alkali metals, potassium graphite or alkali metal
naphthalenides are required (especially when reducing compound 2-4Tip). Before testing our
60
initial hypothesis, we decided to isolate and characterize the mono and direduced species of
compounds 2-4Tip and 2-5Tip in order to study their photophysical and electronic properties.
Table 3-2 Electrochemical data for 2-4Tip and 2-5Tip
2-4Tip 2-5Tip
Epc [a] –2.47, –2.89 –1.52, –2.66
E1/2 [a] ---- –1.45 [b]
[a]
Reduction potentials vs Fc/Fc+. [b] Reversible if potential does not exceed –1.75 V
3.2.1 One-electron chemical reduction
Addition of one equivalent of potassium graphite123,125 into a THF solution of 2-4Tip
resulted in an immediate colour change of the solution from bright yellow to dark violet.
Compound 3-2Tip was crystallized as extremely air and moisture sensitive dark purple crystals by
slow diffusion of hexanes into a THF solution of the product. Likewise, addition of one
equivalent of potassium graphite to a THF solution of 2-5Tip affords air and moisture sensitive
deep blue crystals of 3-3Tip after crystallization using the same solvent mixture (Scheme 3-4).
Despite the different methods used to crystallize compounds 3-2Tip and 3-3Tip, X-ray quality
crystals for structural characterization of the monoanions were not obtainable. It is well know
that crystallization of radical anions is not an easy task, not only because the inherent instability
of the radical species,153 but also because the solvent plays a crucial role stabilizing the alkali
metal counter cation.154,155 Furthermore, the solvation of cations can influence the interrelated
61
equilibria of electron transfer, ion pair formation, or aggregation, controlling the crystallization
process.156,157
(THF)n (THF)n
K Tip K Tip CoCp*2 Tip

B B
B
B
B
Tip B
3-2Tip Tip 3-3Tip
Tip
3-4Tip, 35%
l2
*
2
2C
Cp
1 eq. KC8 THF 1 eq. KC8
CH
THF
Co
or
F
TH
Tip
Tip
B
B Tip =
B B
Tip Tip
2-4Tip 2-5Tip
Scheme 3-4 Synthesis of radical anions 3-2Tip, 3-3Tip and 3-4Tip
3.2.1.1 EPR Characterization
Although the compounds could not be characterized by X-ray diffraction, radical anion
formation was confirmed by electron paramagnetic resonance (EPR) spectroscopy, which in both
cases showed broad featureless resonances, located at giso = 2.00279 for 3-2Tip and giso = 2.00248
for 3-3Tip. These giso values are in the range expected for organic π-radicals158-161 and no
hyperfine coupling could be resolved in each case, even at low temperatures. However, clear
hyperfine coupling was observed in the EPR spectrum of 3-2Tip when the radical was generated
in situ by addition of 2-4Tip to a THF solution of the direduced species 3-5Tip (vide infra). An
62
analogous comproportionation experiment using 2-5Tip and 3-6Tip failed to reveal a resolvable
hyperfine splitting pattern in this case.
EPR Spectrum EPR Spectrum
SOMO SOMO
Spin Density Spin Density
3-2Tip 3-3Tip
Figure 3-2 Overlap of the experimental and simulated EPR spectrum of 3-2Tip (left) and 3-3Tip
(right). SOMO and spin density (UB3PW91/6-31+G(d)) of 3-2Tip (left) and 3-3Tip (right)
Due to the complicated nature of the EPR spectrum of 3-2Tip and the lack of information
from the EPR spectrum of 3-3Tip, the structures of both radical anions were modelled by DFT
63
computations using the UB3PW91 functional with the 6-31+G(d) basis set.†† The optimized
structures were used to calculate the hyperfine coupling constants (hfcc) using the EPR-II basis
set developed by Barone.163 This basis set is optimized for the computation of hyperfine coupling
constants by DFT methods.163 The hyperfine coupling constants were used as the initial values
for the simulations of the EPR spectrum using the program PEST Winsim.164 The hfcc were then
modified by hand until the correlation between the simulated and the experimental spectra was
higher than 97%. Subsequently, the “optimization” function of the program was utilized to reach
a correlation of 99.6% for 3-2Tip and 99.9% for 3-3Tip. The computed hyperfine coupling
constants are in reasonable agreement with the experiment (Table 3-3), except for a(11B).
Nonetheless, previous work by Curran,165,166 and our own experience, have shown that computed
a(11B) values depend strongly on the basis set employed. The hyperfine coupling constants
a(11B) in 3-2Tip and 3-3Tip of 1.08 G and 0.55 G, respectively, are lower than those observed in
other organic boron containing π-radicals (usually between 3.5 and 6 G),158,162,167,168 indicating
that the spin density is away from the boron center into the aromatic rings. This is in contrast to
EPR studies of the one-electron reduced triarylboranes where the unpaired electron is mainly
localized on the boron center.169-172 The SOMO shows a high degree of delocalization, which can
also contribute to the lowering of the hyperfine coupling constants (Figure 3-2). Interestingly,
although the triisopropylphenyl (Tip) groups on boron are essentially perpendicular to the ligand
framework (Figure 3-3), hyperfine coupling to the isopropylmethine protons, HV, which are
located above and below the boron center, is present. Yamaguchi has demonstrated the
††
The theoretical calculations were performed using the Gaussian 09 program. This functional was chosen because
the Yamaguchi group has successfully used it to optimize radical structures containing a boron center.(162) Kushida,
T.; Yamaguchi, S. Organometallics 2013, 32, 6654.
64
interaction of these protons with a planar π-system and has used this feature to assess the
antiaromaticity in benzoborole-fused benzothiophenes.105
Table 3-3 Calculated and simulated ∣hfcc∣ of 3-2Tip and 3-3Tip (in gauss)
Hx
Hw Hw Tip
Tip Hx
Hy B
B
Hy
Hz Hv B
Hv B
Hz
3-2Tip 3-3Tip
3-2Tip 3-3Tip
Element # Nuclei Calc.a Sim.b Calc.a Sim.b
11
Bc 2 3.75 1.08 1.87 0.55
1
Hz 2 2.54 3.72 0.89 0.98
1 y
H 2 0.89 0.89 0.30 0.26
1
Hx 2 1.41 1.80 1.10 1.21
1
Hw 2 2.12 1.81 0.01 0.01
1
Hv 4 0.70 0.70 0.49 0.41
a
Geometries were optimized using UB3PW91/6-31+G(d) and the hfcc were calculated using
UB3PW91/EPR-II. b Simulated using PEST Winsim to >99% correlation. c 10B was not included
in the simulation.
The remarkable ability of the bis(triphenylphosphine)iminium (PPN+) cation to stabilize
air-sensitive anions and to facilitate their structural determination173-178 motivated us to exchange
the potassium cation for bis(triphenylphosphine)iminium (PPN+) via salt metathesis in an effort
to structurally characterize species 3-2Tip and 3-3Tip. In both cases, these experiments resulted in
65
decomposition. However, since the first reduction potential of compound 2-5Tip is considerably
lower than that of 2-4Tip, it was possible to carry out a one-electron reduction of 2-5Tip using the
milder reducing reagent bis-(pentamethylcyclopentadienyl)cobalt(II) (Cp*2Co) in THF or
CH2Cl2.67,68,127,167 Addition of one equivalent of Cp*2Co to a dichloromethane solution of 2-5Tip
immediately produced the characteristic deep blue colour observed in 3-3Tip. Furthermore, the
EPR signal of the new species was similar to the one observed for 3-3Tip. In the freezer at –30 ºC,
the solvent was slowly removed by vapour diffusion into toluene and deep blue X-ray quality
crystals were deposited after several days, confirming the structure of the radical anion (Figure
3-3).
3.2.1.2 X-ray crystallography
The molecular structure of 3-4Tip is shown in Figure 3-3. When compared to its neutral
counterpart, compound 3-4Tip showed a lengthening of the C1-C1’ bond (1.410(3) Å for 3-4Tip vs
1.367(5) Å for 2-5Tip) and a shortening of the B1-C1 bond (1.524(4) Å for 3-4Tip vs 1.571(4) Å
for 2-5Tip). These bond length changes are also consistent with the nature of the SOMO as
revealed by the DFT computations (Figure 3-2) because the SOMO contains a node in the C1-
C1’ bond and has π-bonding character along the B1-C1 vector. The largest deviation from the
mean plane defined by the core B2C6 atoms (fused borole rings) amounts to 0.032(3) Å, showing
that the π-system in 3-4Tip remains planar after reduction. This is in contrast to the planarized
triarylborane radical anion reported by Yamaguchi162 and the dibenzo(a,e)pentalene radial anion
reported by Saito.179 These examples both adopt a shallow bowl-shaped conformation after
66
reduction with potassium, which reflects the high degree of delocalization of the unpaired
electron throughout the B2C14 framework of the ladder diborole.
atoms and Cp*2Co have been removed for clarity

C1-B1 1.524(4) C2-B1-C8 126.6(2)
B1-C2 1.586(4) C2-B1-C1 102.3(2)
C1-C1’ 1.410(3) C8-B1-C1 131.0(2)
C3-C1’ 1.470(4) C1-C1’-C3 109.0(2)
C2-C3 1.420(3) C1-B1-C3’ 140.3(2)
C3-C4 1.389(3)
C5-C6 1.386(4) C2-B1-C8-C13 –68.1(4)
C6-C7 1.390(4) C4-C3-C1’-C1 179.4(3)
C7-C2 1.379(4)
67
3.2.2 Two-electron chemical reduction
Having demonstrated facile one-electron reduction of both compounds 2-4Tip and 2-5Tip,
we turned to preparing the dianionic species that would be isoelectronic to the all-carbon
frameworks 3-I and 3-II shown in Scheme 3-1. A freshly prepared green THF solution of
potassium naphthalenide180-182 (2 eq.) was slowly added to a solution of the respective starting
materials 2-4Tip and 2-5Tip in THF at –78 ºC. After stirring the solutions for an additional two
hours at room temperature, the solvent was evaporated and the naphthalene removed by
sublimation under high vacuum. Compound 3-5Tip was isolated as a dark brown solid after
crystallization in THF and hexanes in 60% yield, and compound 3-6Tip as red crystals from the
same solvent mixture in 55% yield (Scheme 3-5).
THF
Tip Tip
K
B B
2 eq. KNaph
B B
THF K
Tip Tip
2-4Tip THF 3-5Tip, 60%
THF
Tip
Tip
B K
2 eq. KNaph B
THF B
B
Tip Tip K 3-6Tip, 55%
2-5Tip THF
Scheme 3-5 Synthesis of 3-5Tip and 3-6Tip
68
3.2.2.1 Nuclear Magnetic Resonance (NMR) Spectroscopic Analysis
The 1H NMR spectrum of compound 3-5Tip isolated in this way is intriguing. All the
signals are broad and it is not possible to distinguish any fine structure from the coupling with
adjacent protons (Figure 3-4). Furthermore, the chemical shifts of the aromatic protons (except
for the resonance belonging to the Tip group) are shifted considerably upfield (between 5.5 and
4.2 ppm) from where they are expected to resonate. Since the second reduction potential of
compound 2-4Tip is very negative, we surmised that 3-5Tip might be contaminated with small
amounts of the radical anion 3-2Tip, resulting in the broadness observed in the 1H NMR
spectrum.
EPR spectroscopy on isolated samples of 3-5Tip confirmed the presence of 3-2Tip.
Furthermore, augmentation of the signal was observed upon addition of small aliquots of 2-4Tip
to the EPR sample (see Figure 3-5) due to the in situ formation of the radical 3-2Tip. This
experiment also shows that the direduced compound 3-6Tip is a good electron donor and is
capable of reducing another chemical species.‡‡ In contrast to the broadening observed in the 1H
NMR spectrum, in the 13C{1H} NMR spectrum of 3-5Tip minimal broadening was apparent, and
all the resonances are clearly identified. Even the resonances for the carbons bonded to the boron
center appear as small broad peaks, and their identity was confirmed by 1H-13C Heteronuclear
11
Multiple-Bond Correlation (HMBC) spectroscopy. The B NMR spectrum shows a broad
resonance at 38.7 ppm which is well within the range of values observed for 9-phenyl-9-
borataanthracene (39.7 ppm)183 and other boratabenzene anions.60,183-188 This signal is shifted
‡‡
The same applies for 3-6Tip because it is capable of reducing 2-5Tip.
69
considerably upfield compared to the resonance of 2-4Tip (70.1 ppm), which is consistent with a
more electron-rich boron center.
Tip
B
Figure 3-4 1H NMR spectrum of compound 3-5Tip (THF-d8, 600 MHz)
70
THF (THF)n
Tip Tip
K K Tip
B B
+ B
B THF
K B B
Tip
Tip Tip
THF 3-5Tip 2-4Tip 3-2Tip
indicate a qualitative increment in the amount of compound 2-4Tip added to the EPR tube
containing 3-5Tip
Unlike the 1H NMR spectrum of 3-5Tip, there is no broadening of the signals in the
spectrum of 3-6Tip and all the coupling between neighbouring hydrogen atoms is observed.
Furthermore, all the resonances appear in the expected region of the spectrum. The resonance for
the aromatic Tip protons remains practically unchanged after direduction (7.04 ppm for 2-5Tip
and 6.94 ppm for 3-6Tip); however, the aromatic protons of the main framework shift slightly
upfield, perhaps due to a change in the ring current effect from a 14 π-electron aromatic system
to an 16 π-electron antiaromatic system.87,96 The average chemical shift for the aromatic protons
in 2-5Tip is 6.87 ppm and 6.45 ppm in 3-6Tip. The isopropyl methine proton situated above the
71
boron center experiences a more severe chemical shift change due to the addition of electrons in
the π-system. In compound 2-5Tip, the isopropyl methine proton chemical shift is at 2.70 ppm,
but in 3-6Tip the resonance is shifted downfield by 0.71 ppm (3.41 ppm). Similarly, the chemical
shift for the olefinic carbon bridging the borole rings moves from 141.58 ppm in 2-5Tip to 134.20
ppm in 3-6Tip, consistent with a more electron rich environment. The boron chemical shift for the
ladder diborole dianion 3-6Tip appears at 32.1 ppm, shifted slightly upfield compared to 3-5Tip
(38.7 ppm). However, this resonance is very close to the chemical shifts reported for borole
dianions (~30 ppm)48,189-191 and is again considerably shifted upfield compared to the neutral
precursor 2-5Tip (68.6 ppm).
2– 2–
2–
B B
B
Cl
SiMe3
11B 29.6 ppm 11B 11B
28.7 ppm 26.6 ppm
Figure 3-6 11B chemical shifts of several borole dianions
72
Tip
B
Figure 3-7 1H NMR spectrum of compound 3-6Tip (THF-d8, 600 MHz)
3.2.2.1.1 X-ray crystallography
X-ray analysis of single crystals of 3-5Tip reveals the structure of the dianionic species
(Figure 3-8). The largest deviation from the mean plane defined by the B2C6 core atoms amounts
to 0.010(3) Å, showing that compound 3-5Tip remains planar after direduction. The boron center
adopts a distorted trigonal planar geometry, with a small C7-B1-C1 angle of 87.49(12)º due to
the constrained four-membered ring. There are two potassium atoms situated on opposite sides of
73
the π-system, coordinating to the bay regions on either side of the central C1-C1’ bond. The
distance between the potassium centers and the B1-C1-C1’-B1’ plane is 2.623 Å. There are three
molecules of THF coordinated to each potassium center (not shown in Figure 3-8); however,
based on 1H NMR spectroscopy and elemental analysis only one solvent molecule per metal
remains coordinated when the crystals are placed under vacuum.
atoms and THF molecules have been removed for clarity
74

C1-B1 1.504(3) C7-B1-C1 87.49(12)
B1-C7 1.629(4) C7-B1-C8 131.9(2)
C8-B1 1.592(3) C8-B1-Cl 140.5(2)
C2-C3 1.376(3) B1-C1-C1’ 145.5(2)
C3-C4 1.426(3)
C4-C5 1.358(4)
C5-C6 1.41642) Dihedral Angles (º)
C6-C7 1.367(4) C2-B1-C8-C13 –68.1(4)
C7-C2 1.437(3) C4-C3-C1’-C1 179.4(3)
C2-C1 1.492(3)
While the bond angles within the molecular core do not change drastically upon
reduction, the bond distances in the diboratacyclobutylidene π-system change significantly. For
example, in neutral starting compound 2-4Tip, the B1-C1 bond distance is 1.581(5) Å, which is
indicative of a B-C single bond, but in compound 3-5Tip the B1-C1 bond distance is considerably
shorter (1.504(3) Å) suggesting double bond character.118,135,192,193 Similar B=C values have been
reported for 9-phenyl-9-borataanthracene (1.532(3) Å)183 and 9-boraanthracene (1.507(4) Å).74
Conversely, the C1-C1’ distance in neutral 2-4Tip (1.330(7) Å) is consistent with a C=C double
bond, but in 3-5Tip the distance is considerably longer (1.437(3) Å) which is indicative of a Csp2-
Csp2 single bond.118,194 These observations are entirely consistent with the characteristics of the
LUMO of 2-4Tip and the SOMO of 3-2Tip revealed by computations as they both contain a node
along the C1-C1’ bond and π bond contribution along the B1-C1.
75

C1-B1 1.479(4) C1-B1-C3 102.2(2)
B1-C3 1.586(4) C3-B1-C8 125.6(2)
C8-B1 1.608(3) C8-B1-Cl 132.3(2)
C2-C3 1.408(3) B1-C1-C1’ 112.7(2)
C3-C4 1.368(4)
C4-C5 1.400(4)
C6-C7 1.390(4) C3-B1-C8-C13 –67.7(3)
C7-C2 1.433(3) C7-C2-C1-C1’ 179.5(2)
C2-C1’ 1.479(3)
76
X-ray crystal structure analysis of compound 3-6Tip shows a sandwich complex (Figure
3-9), with the potassium atoms situated just above and below of the center of the pentalene
framework in a centrosymmetric arrangement. The largest deviation from the mean B2C6 plane is
only 0.010(3) Å. The separation between the two potassium atoms measures 5.506 Å, which is
similar to the value found in a B4N2C2 sandwich complex (5.52 Å) reported by Roesler et al.195
In the X-ray structure there are two THF molecules per potassium center (not shown in Figure
3-9), but only one solvent molecule remains coordinated when the crystals are placed under
vacuum. Similar to compound 3-5Tip, the C1-B1 (1.479(4) Å) and C1-C1’ (1.466(3) Å) bond
distances are indicative of a double and single bond character respectively.118,135,193,194 As
anticipated, the C1-C1’ bond distance in 3-4Tip is of intermediate length between the C1-C1’
double bond shown in 2-5Tip (1.367(5) Å) and the single bond in 3-6Tip (1.466(3) Å). Likewise,
the B1-C1 bond distance is between that of the B1-C1 single bond for 2-5Tip (1.571(4) Å) and the
double bond in 3-6Tip (1.479(4)) Å. This clearly illustrates how changing electronic structure of
the molecule upon one- and two-electron reduction impacts the physical structure and the
bonding motif of the π-system in 2-5Tip. Even though there is a significant difference in the
bonding order in C1-B1 and C1-C1’ between 2-5Tip and 3-6Tip, the other bonds in the borole
rings remain practically unchanged (Figure 3-10). This suggests that there is no significant
difference in the bond alternation in the direduced compound compared to the neutral one, which
is the opposite to the observations on boroles and direduced boroles.191 In the latter, this was
attributed to the formation of an aromatic system after reduction.
77
1.480(4) 1.479(3)
9(3)
0(3)
1.46
1.36
1.41
1.48
6(3)
7(5)
1. 1. )
58 4) 58 (4
1(
8(
4) B 1.
57
6(
4) B 1.479
Tip Tip
2-5Tip 3-6Tip
Figure 3-10 Bond distance (Å) comparison between the borole rings in 2-5Tip and 3-6Tip
3.3 Absorption and Fluorescence Spectroscopy
Compound 3-5Tip is dark brown in the solid state and in solution (THF). In contrast to
neutral 2-4Tip, 3-5Tip is not emissive under UV-light and its absorption spectrum is considerably
red-shifted (Figure 3-11), with the longest absorption maximum at 802 nm (ℇ = 9640 M−1 cm−1).
TD-DFT calculations (B3LYP/6-31G(d), td=(states=20)) on 3-5Tip accurately reproduce the
experimental absorption spectrum and show that this energy transition can be attributed to a
transition from HOMO to LUMO (calcd: 805 nm, f = 0.1468) and is mainly π→π* in character
(Figure 3-12).
Compound 3-6Tip exhibits a magenta colour in solution (THF) and displays purplish pink
emission under UV light (λmax = 620 nm). In contrast, the precursor 2-5Tip is non-fluorescent
under UV light. Compound 3-5Tip shows major peaks at 531 nm, 352 nm, 337 nm and a shoulder
at 507 nm in the absorption spectrum (Figure 3-11). Based on TD-DFT calculations (B3LYP/6-
311G(d)), the longest absorption band is mainly comprised of the HOMO-LUMO transition
78
(calcd: 485 nm, f = 0.2530) and is mostly π→π* in character (Figure 3-12). Compound 3-6Tip
has the same number of π-electrons as dibenzopentalene 3-III (Figure 3-13), however, the
former is non-emissive under UV-light and the longest absorption maximum is around 450
nm.196 Interestingly, the longest absortion maximum in compound 3-6Tip is red-shifted not only
compared to the carbon analogue dibenzopentalene 3-III, but also compared to pentalene
derivatives with a more extended π-system, such as benzonaphthopentalene (3-IV) and
dinaphthopentalene (3-V). The longest absorption maximum for compound 3-IV is around 470
nm and for compound 3-V around 500 nm.29 This clearly shows that exchanging carbon for a
more electropositive boron atom causes a significant change in the electronic and photophysical
properties of conjugated π-systems.
Figure 3-11 Absorption and emission spectrum of compounds 3-5Tip and 3-6Tip in THF. Blue
line: 3-5Tip absorption; red line: 3-6Tip absorption; dotted red line: 3-6Tip emission.
79
LUMO LUMO
B B (THF)2
K K (THF)3 K
B Tipp
(THF)3 B Tipp (THF)2
HOMO HOMO
3-5Tip 3-6Tip
Figure 3-12 HOMO and LUMO orbitals of compounds 3-5Tip and 3-6Tip
Ph Ph Ph
Ph Ph Ph
3-III, 450 nm 3-IV, 470 nm 3-V, 500 nm
Figure 3-13 Several pentalene derivatives and their longest absorption maxima
3.4 Aromaticity and antiaromaticity. Nucleus Independent Chemical Shift (NICS)

Calculations
Whereas the ladder diborole 2-5Tip is a 14 π-electron aromatic system, introduction of
another electron pair should give the 16 π-electron dianion 3-6Tip antiaromatic character. To
evaluate this notion, we carried out NICS calculations (B3LYP/6-311+G(d,p))85,97 on the dianion
80
of 3-6Tip and dibenzopentalene 3-III197 (Table 3-7). The central five-membered rings in dianion
3-6Tip possess antiaromatic character (NICS(0) = 6.1, NICS(1) = 1.3) and the flanking benzene
rings (NICS(0) = –0.9, NICS(1) = –3.9) are considerably less aromatic than benzene itself
(NICS(0) = –9.7). However, the antiaromatic character of the borole rings in 2-5Tip (NICS(0) =
14.9, NICS(1) = 6.3) clearly decreases after the addition of two electrons. Likewise, the aromatic
character of the flanking benzene rings in 2-5Tip increases (NICS(0) = –3.2, NICS(1) = –6.2).
Interestingly, dibenzopentalene 3-III possesses a stronger antiaromatic character on the central
rings (NICS(0) = 10.4, NICS(1) = 5.8), and a stronger aromatic character on the benzene rings
(NICS(0) = –2.6, NICS(1) = –5.6). This suggests that dibenzopentalene has a more localized π-
system than 3-6Tip;85 nonetheless, it is clear that these two isoelectronic π-systems are closely
related.
Table 3-7 NICS (1/0) values for 2-5Tip, 3-6Tip and 3-III
Tip Tip Ph
B B
a a
b b a
b
B B
Tip Tip Ph
2-5Tip 3-6Tip 3-III
Ring 2-5Tip 3-6Tip 3-III

a –3.2/–6.2 –0.9/–3.9 –2.6/–5.6
b 14.9/6.6 6.1/1.3 10.4/5.8
81
3.5 Thermal Isomerization
With dianions 3-5Tip and 3-6Tip in hand, we set out to test our initial hypothesis that 3-5Tip
might be thermally isomerized to the more stable 3-6Tip using Brønsted acid catalysis. Upon
dissolution of compound 3-5Tip in degassed THF-d8 without rigorous drying (“wet”), the
solution immediately changed from dark brown to deep red; the 1H NMR spectrum clearly shows
formation of substantial quantities of 3-6Tip, along with other hydrolysis products. The reaction
was therefore performed under more controlled conditions in dry solvents using various
measured amounts of 2,6-dimethylphenol as the proton source. This phenol was chosen as the
Brønsted acid because the compound is a solid, it is easy to purify by sublimation, and the
methyl groups are a good NMR handle. After optimizing the conditions, it was determined that a
20% loading of 2,6-dimethylphenol at 75 ºC in THF solution gave compound 3-6Tip, which could
be isolated in 80% yield after stirring for 8 hours under these conditions. However, measureable
amounts of a contaminant were always present. This species was determined to be the doubly
protonated neutral compound 3-7Tip (Scheme 3-6), which can be separately synthesized by
treating 3-6Tip with stoichiometric quantities of the acid. Thus, when two equivalents of 2,6-
dimethylphenol are added to a THF solution of 3-6Tip, the solution changed from red to light
yellow, forming the air and moisture stable 3-7Tip (Scheme 3-6). After removal of the solvent
and extraction/crystallization from hexanes, this compound was isolated as a white solid in 72%
yield. The 1H NMR spectrum shows formation of only one isomer; DFT calculations (M062X/6-
311+G(d,p)//B3LYP/6-31G(d)+ZPE)198 show that the cis isomer is 17.6 kcal/mol more stable
than the trans isomer, and further characterization via NMR spectroscopy and X-ray
crystallography indicates that indeed the cis isomer is formed exclusively. The X-ray structural
82
analysis (Figure 3-14) confirms that the polycyclic ring framework is significantly bent as a
result of the addition of the two hydrogen atoms. C1 adopts a distorted tetrahedral geometry,
with B1-C1-C9, C9-C1-C1’, C1’-C1-B1 angles of 115.2(4)º, 105.4(3)º and 105.5(4)º
respectively, and the torsion angle C2-C1’-C1-C9 is 131.2(4)º. The C1-C1’ bond distance is
considerably longer (1.551(6) Å) than for 2-5Tip (1.367(5) Å) and 3-6Tip (1.466(3) Å), reflecting
the Csp3-Csp3 single bond character.118,194
OH
THF THF
Tip Tip
2 eq. KNaph K Tip
B K
B (20%) B
B B
THF, 75 ºC B
Tip K
Tip
2-4Tip 3-5Tip Tip K
THF
3-6Tip, 84% THF
t-BuOH (xs) THF, RT OH

2 eq.
Tip THF
Tip
B K H Tip
2 eq. AgOTf B H
2 eq. t-BuOK B
B B
B
Tip Tip K Tip
2-5Tip, 69% 3-6Tip, 90% THF 3-7Tip, 72%
Scheme 3-6 Isomerization of 3-5Tip to 3-6Tip, synthesis of 3-7Tip and generation of 2-5Tip via
oxidation of 3-6Tip
83

C1-B1 1.589(7) C1-B1-C3 105.4(4)
B1-C3 1.548(7) C3-B1-C8 131.2(4)
C8-B1 1.557(7) C8-B1-Cl 123.4(4)
C2-C3 1.388(6) B1-C1-C9 131.2(4)
C3-C4 1.388(7)
C4-C5 1.378(6)
C6-C7 1.382(7) C3-B1-C8-C13 –98.0(6)
C7-C2 1.384(6) C2-C1’-C1-C9 131.2(4)
C2-C1’ 1.508(6)
84
The NMR spectra revealed important structural and electronic features of 3-7Tip (Figure
3-15). The characteristic singlet belonging to the bridgehead protons appears at 4.16 ppm. In
contrast to compounds 3-5Tip and 3-6Tip, the 1H NMR spectrum of 3-7Tip clearly shows 6 sets of
signals for the isopropyl methyl protons and 3 sets of signals for the isopropyl methine protons.
The patterns observed for the isopropyl groups on the Tip group in the 1H NMR are in agreement
with the fact that the planarity of the system has been ruptured. One of the methine resonances is
shifted significantly upfield compared to the other two (1.29 ppm vs 2.93 and 2.65 ppm). Since
one of the isopropyl groups is situated under the flanking benzene ring (see Figure 3-14), this
upfield shift was attributed to the ring current effect.96,199 The induced magnetic field in the
center of the benzene ring opposes the external field (paratropic ring current), and the protons
experience additional shielding; which causes an upfield shift.87,96,199,200 The methyl signals of
this isopropyl group are also shielded due to the same effect. Since the central carbons joining
the borole rings are no longer sp2 hybridized, the electron delocalization in the entire framework
is broken. This is reflected in the change in chemical shift of the boron centers. Due to the
decrease in electron density, the boron chemical shift appears at 77.1 ppm, considerably
downfield compared to 2-5Tip (68.6 ppm) and 2-4Tip (70.1 ppm), but very close to more electron
deficient three coordinate boron centers in triarylboranes and phenylboranes.133,134,201
85
H Tip
H
B
B
Figure 3-15 1H NMR spectrum of compound 3-7Tip (CD2Cl2, 600 MHz)
Attempts to doubly deprotonate compound 3-7Tip using potassium 2,6-dimethylphenoxide
to regenerate 3-6Tip were not successful, indicating that protonation by phenol is irreversible.
However, addition of potassium t-butoxide to 3-7Tip did generate 3-6Tip essentially
quantitatively, and this salt was stable in the presence of t-BuOH. Thus, the more weakly acidic
alcohol (pkat-BuOH = 17.0, pka2,6-dimethylphenol = 10.0)202,203 was used in excess to convert 3-5Tip to
3-6Tip on a preparative scale, avoiding contamination by 3-7Tip and providing 3-6Tip in excellent
yield (Scheme 3-6). The entire isomerization process can be followed by NMR spectroscopy
(Figure 3-16).
86
after 60 min
(3-6Tip)
after 40 min
after 10 min
3-5Tip
Figure 3-16 Isomerization of 3-5Tip to 3-6Tip after addition of 2 equivalents of t-butanol (THF-
d8, 600 MHz).
The route to prepare 3-6Tip was successfully optimized and it was possible to isolate
relatively high amounts (≈ 100 milligrams) of the dianionic species 3-6Tip, skipping the synthesis
of benzoborole-fused benzoborole 2-5Tip, as it was proposed in our initial hypothesis. Now the
reaction to close the cycle and actually isolate 2-5Tip from 3-6Tip had to be tested. Compound 3-
6Tip was reacted with silver triflate at –78 ºC in THF. The solution immediately changed from
red to dark blue, and after a couple of seconds to dark green. The resulting mixture was allowed
to reach room temperature over half an hour; the solution slowly turned brownish green. After
evaporation of the solvent, the brownish green solid was recrystallized in dichloromethane and
87
hexanes providing dark green crystals of 2-5Tip in 69% yield, successfully completing a thermal
synthesis of 2-5Tip from 2-4Tip as planned (Scheme 3-6).
3.5.1 Proposed mechanism
This type of isomerization is new for a boron containing heterocycle, but we have
proposed an analogous mechanism to the one proposed for the carbon analogue 3-I (Scheme
3-1). However, instead of a carbocation as the key species in the rearrangement, the Lewis acidic
boron center triggers the bond migrations that occur upon protonation of the framework (Scheme
3-7). To understand in more detail the mechanism of this rearrangement, the reaction pathways
were investigated by geometry optimization of the possible intermediates and transition states
(Scheme 3-7). The transition state was verified by intrinsic reaction coordinate (IRC)
calculations.204-206 The optimized structures of intermediates IA, IB and the transition state TS are
shown in Figure 3-17 for easier visualization of the structural geometries (compared to
Chemdraw drawings in Scheme 3-7).
Intermediate IA is formed after protonation of one of the benzylic carbons in 3-5Tip by the
alcohol. This intermediate is considerably bent because the newly protonated C1 changes
hybridization from sp2 to sp3, which leaves the electrophilic boron center closer to the
nucleophilic olefin (B1-C1’ distance is 1.6870 Å). A nucleophilic attack and a bond breaking
between the boron center and the recently protonated carbon might take place. Intermediate IB is
produced after a series of rearrangements through the transition state TS, releasing some of the
88
strain in the four-membered heterocycles (the B1-C1’-C1 angle changes from 60.86º in IA to
105.57º in IB). The conjugate base (alkoxide) deprotonates IB forming compound 3-6Tip and
regenerating the acid catalyst (alcohol). When the acid is a phenol, this species can be
irreversibly protonated to give 3-7Tip; thus we surmise that IB is itself acidic enough to protonate
3-5Tip to induce the ring expansion rearrangements, or the reaction would stop at this point in the
phenol catalysed processes. For the t-BuOH mediated process, this is not an issue, since this
alcohol is not acidic enough to protonate 3-6Tip (pkat-BuOH = 17.0, pka2,6-dimethylphenol = 10.0).202,203
Tip
Tip H Tip H B
H B B
B B B
Tip Tip Tip
IA [0,0] TS [3,4] IB [-54,0]
+ KOR
+ HOR - HOR
- KOR
Tip
Tip
B
B + HOR
- KOR
B B
Tip Tip
3-5Tip [0,0] 3-6Tip [-74.8]
Scheme 3-7 Proposed mechanism for the rearrangement of 3-5Tip. Numbers in brackets indicate
the energies (kcal mol-1) of the species relative to IA (in black) and 3-5Tip (in gray) (SCS-MP2/6-
311+G(d,p)//B3LYP/6-31G(d)+ZPE)
89
B2
C1 C2
B2 C2
C3 C4 C1 C2 B2 C1
C3 C4
B1 C3
B1
B1
IA TS IB
B2
B2
C1 C1 C2
C3
C2 C3 C4
C4
B1 B1
3-5Tip 3-6Tip
Figure 3-17 Optimized structures of compounds 3-5Tip and 3-6Tip, intermediates IA, IB and the
transition state TS. Hydrogen atoms have been removed for clarity
Attempts to generate IB through protonation of 3-6Tip with one equivalent of a strong acid
(thereby generating a weak conjugate base not capable of deprotonating IB) such as triflimidic
acid (HNTf2) were not successful.207,208 The only products observed in the 1H NMR spectrum
were 3-6Tip and 3-7Tip in a 1:1 mixture; this indicates that IB is a very reactive species, both as an
acid and a base. Since compound 3-7Tip could potentially be a precursor for 2-5Tip via
90
dehydrogenation, different conditions and reagents such as Pd/C were tested,209,210 but there was
no indication of dehydrogenation.
This chapter described the synthesis, characterization and preliminary reactivity studies of
3-5Tip, which was synthesized by direct reduction of 2-4Tip with potassium naphthalenide. In the
course of these studies, it was found that the persistent radical anions 3-2Tip, 3-3Tip and 3-4Tip,
formed upon one-electron reduction, could be generated and characterized. In the case of 3-4Tip,
an X-ray structural determination was possible, allowing for a detailed analysis of the bond
length changes in the conjugated framework upon sequential one- and two- electron reduction.
As postulated in the initial hypothesis, 3-5Tip undergoes an acid-catalyzed isomerization to form
3-6Tip. It was found that t-BuOH is the best reagent for inducing this skeletal rearrangement since
more acidic phenols can doubly protonate 3-6Tip to form compound 3-7Tip as an air and moisture
stable white solid. The 16 π-electron diborole dianion 3-6Tip was shown to have less antiaromatic
character (NICS calculations) than the neutral diborole 2-5Tip. The exchange of the carbon atom
in dibenzopentalene for a boron center dramatically changed the photophysical properties of the
conjugated framework. Compound 3-6Tip shows a drastic red shift in the absorption spectrum
compared to dibenzopentalene and, unlike the former compound, shows a purplish pink emission
under UV light. More importantly, compound 3-6Tip can be oxidised using silver triflate.
Therefore, we have discovered another path for the synthesis of compound 2-5Tip, which is more
91
reliable than the photochemical isomerization reported in Chapter two. This has been the method
of preference lately for the preparative scale synthesis of 2-5Tip in our group.
92
Chapter Four: Borole ring-expansion by addition of CO and CO2
4.1 Introduction
The growing interest in the chemistry of antiaromatic boroles has led to remarkable
progress in the past few years in terms of understanding the properties of these molecules and
incorporating the borole core into more complex systems.47,49,143,211,212 One of the most common
modes of reactivity involves reactions that expand the antiaromatic five-membered ring to larger
rings in which both strain and antiaromaticity are alleviated. The first ring-expansion of this five-
membered boracycle was reported almost 40 years ago.213 Eisch observed that a suspension of
pentaphenylborole and diphenylacetylene undergoes Diels-Alder cycloaddition accompanied by
a colour change from dark blue to colourless. The cycloaddition product was characterized as
compound IV-1, which underwent a sigmatropic rearrangement at high temperatures forming
intermediate species IV-2. A disrotatory ring-opening reaction of species IV-2 ultimately formed
compound IV-3, which was isolated as a bright yellow solid (Scheme 4-1).45,213-215
Ph
Ph B Ph
Ph Ph
Ph Ph Ph
Ph Ph toluene, RT
B
Ph Ph Ph
Ph IV-1
toluene
120 ºC
Ph Ph Ph
Ph Ph
Ph Ph
B Ph
B Ph Ph
Ph Ph
Ph Ph
IV-3 IV-2
Scheme 4-1 Ring-expansion of pentaphenylborole213
93
Following Eisch’s seminal report, the reactivity of boroles was sparsely explored for
almost four decades. However, this chemistry has been revitalized in recent years due to the
elucidation of the solid-state structure of pentaphenylborole and the development of improved
synthetic routes to new borole derivatives.49,216-218 For example, early in 2014, the Braunschweig
group reported the synthesis of 1,2-azaborinines210,219 by ring-expansion of boroles.220 The
compounds were prepared by direct reaction between organic azides and the borole derivatives
with the concomitant release of nitrogen (Scheme 4-2). When pentaphenylborole was treated
with TMS azide, (CH3)3SiN3, the reaction proceeded slowly (22 h) at room temperature,
indicated by a colour change from blue-violet (characteristic of antiaromatic pentaphenylborole)
to colourless. In order to explore the scope of the reaction, the authors performed the same
reaction using the bulkier mesityl substituent on boron. This reaction proceeded significantly
slower at room temperature evidenced by minimal conversion of starting material over the
course of 3 days. The increased steric demand at boron resulted in a sluggish reaction which
required thermal perturbation to proceed at a reasonable rate (60 C for 5 h). Phenyl azide was
also used to produce hexaphenyl-1,2-azaborinine, establishing a new synthetic route to 1,2-
azaborinines deriatives.220
Ph
Ph Ph N R Ph
+ N N
Ph Ph -N2 B
B N Ar Ph
R
Ar Ph
Ar = Ph R = SiMe3, Ph
Ar = Mes
Scheme 4-2 Synthesis of azaborinines via ring-expansion of borole derivatives220
94
Shortly thereafter, Dutton and co-workers investigated the mechanism of the borole ring-
expansion using computational methods (Scheme 4-3).221 In summary, they found that the first
step is coordination of the azide nitrogen to the boron center in borole, followed by subsequent
formation of a bicyclic intermediate, which subsequently releases nitrogen to yield the 1,2-
azaborinine product.
N N Me3Si
N
+ N N
B B -N2 B
B N N Ph
Me3Si N Ph
Ph N SiMe3 Me3Si Ph
N –389 KJ/mol
0 KJ/mol –13 KJ/mol –30 KJ/mol
Scheme 4-3 Dutton’s proposed mechanism for the formation of 1,2-azaboririne product221
Prior to these discoveries, our group reported the reactivity of pentaphenylborole and
perfluoropentaphenylborole with carbon monoxide.222 It was observed that
perfluoropentaphenylborole forms a stable adduct with carbon monoxide at room temperature,
but the coordination of carbon monoxide is reversible. Placing the system under vacuum results
in rapid dissociation of carbon monoxide and regeneration of perfluoropentaphenylborole
(Scheme 4-4).222 The unfluorinated pentaphenylborole also forms an adduct with carbon
monoxide at –78 ºC, but upon increasing the temperature the adduct undergoes a reaction beyond
simple dissociation of the carbon monoxide ligand (Scheme 4-4).222 The authors have postulated
that upon increasing temperature, the carbon monoxide adduct undergoes insertion of the CO
into an intraring B-C bond to form an unstable cyclic acyl borane derivative. This species then
undergoes further transformations to produce a mixture of products, from which tricyclic
boracycle IV-5 was observed by high resolution MALDI-TOF mass spectrometry (Scheme 4-4).
95
O
C6F5 C6F5 C
C6F5 CO C6F5
B C6F5 B
C6F5 vacuum C6F5 C6F5
C6F5 C6F5
O
C6H5 CO C6H5 C
C6H5 –78 ºC C6H5
B Ph B
C6H5 C6H5 Ph
C6H5 C6H5
– 10 ºC
C6H5 Ph C6H5 C6H5

C6H5 O C6H5 C6H5 O
B
B B
C6H5 O C6H5 C6H5 Ph
C6H5 Ph C6H5 C6H5
IV-5
Scheme 4-4 Reaction of pentaarylboroles with carbon monoxide222
Before beginning the discussion of ring-expansion chemistry by the boracycles presented
in this thesis, it is important to mention that azides and alkynes were mixed with the boracycles
2-4Tip and 2-5Tip, but no reactivity was observed even at elevated temperature. Based on the
trends in reactivity of boroles with azides reported by Braunschweig (vide supra), it is likely that
the bulky 2,4,6-triisopropylbenzene group prevents any close interaction of the reagents with the
Lewis acidic boron center, hampering the reactivity. Therefore the choice of the smaller
molecules carbon monoxide and carbon dioxide seemed suitable for the ring-expansion studies,
and these studies will be presented below.
4.2 Addition of carbon dioxide and characterization of insertion products
The neutral ladder diborole 2-5Tip showed no reactivity towards carbon dioxide under
ambient conditions. The chemistry of compound 2-4Tip under one atmosphere of carbon dioxide
96
was a little more puzzling. After addition of carbon dioxide there was no colour change, but the
1
H-NMR spectrum showed a slow formation of the intermediate observed in the
photoisomerization of 2-4Tip under UV light (Figure 2-8). The 2-4Tip/intermediate ratio slowly
increased over time up to 70/30 in 24 hours, after which point the ratio remained constant and
decomposition started to become more evident by NMR spectroscopy. Increasing the
temperature (50 ºC) did not change the ratio of the compounds, but accelerated the
13
decomposition. By performing the experiment using CO2 it was corroborated that there is no
insertion of CO2 into the four-membered ring. As discussed in Chapter two, this suggests that
this species is the product of a cis-trans isomerization of 2-4Tip; in this case promoted by the
addition of carbon dioxide.
Therefore, we turned our attention to the dianionic species 3-5Tip and 3-6Tip as their
electron-rich nature suggested the possibility of favourable reactivity towards CO2. Furthermore,
it is well known that electron-rich species such as Grignard or organolithium reagents add to
carbon dioxide, carboxylic acid derivatives, aldehydes, and ketones due to the electrophilic
nature of the carbonyl carbon.223-226 A resealable NMR tube was charged with 3-5Tip and the
compound was dissolved in THF-d8. The tube was degassed at −78 °C, and CO2 was expanded
into the tube (1 atm). The dark brown solution, characteristic of 3-5Tip, rapidly turned yellow
even at low temperature. The proton NMR spectrum showed clean formation of a new species
and the broad peaks observed in the 1H NMR spectrum of 3-5Tip (Figure 3-4) sharpened (Figure
4-1). Furthermore, the resonances of the aromatic protons moved downfield (the aromatic
protons in 3-5Tip resonate between 5.57 and 4.20 ppm) as shown Figure 4-1. Another clear
indication that the electronic properties of the starting material were significantly modified came
97
from the upfield shift of the ortho-isopropyl methine resonances from 3.58 ppm in 3-5Tip to 2.86
ppm in the new species.
This NMR experiment motivated us to increase the scale of the reaction to 80 mg of
starting material. A THF solution of 3-5Tip was exposed to one atmosphere of carbon dioxide and
the solution was stirred at room temperature for 30 min. The solvent was evaporated leaving a
yellow solid, which was purified by washings with cold pentanes. Any attempts to purify this
solid by recrystallization in different solvent mixtures such as THF or dichloromethane in
hexanes were unsuccessful.
Tip
THF B
Tip O
K
B CO2 (1 atm) KO
B THF OK
Tip K
O 4-1Tip
THF B
3-5Tip 70% (from 3-5Tip)
) Tip 73% (from 3-6Tip)
atm
(1
2
THF CO TH
F
Tip KO
K O Tip
B CO2 (1 atm) B
B THF
Tip K B
Tip O OK
3-6Tip THF
The same procedure using a resealable NMR tube was repeated with a red THF-d8
solution of the ladder diborole dianion 3-6Tip. After addition of carbon dioxide the solution also
turned yellow and NMR spectroscopy showed that this reaction afforded an identical product to
that observed in the reaction of carbon dioxide with 3-5Tip. This result was counterintuitive since
a six-membered ring expansion-product was expected to be formed after the insertion of carbon
98
dioxide into 3-5Tip, whereas a seven-membered ring expansion-product (similar to a borepin
derivative)215,227-229 was expected after the insertion into 3-6Tip as shown in Scheme 4-5. The
NMR spectra of both possible products (six- and seven-membered rings) should show the same
number of resonances and connectivity. This makes 2D heteronuclear chemical shift correlation
maps between directly-bonded and long-range coupled 1H and 13

C of little use when trying to
determine the structure of the product of the reaction. However, DFT calculations (M062X/6-
311+G(d,p)//B3LYP/6-31G(d)+ZPE)198 showed that the six-membered ring 4-1Tip is ≈ 43
kcal mol-1 more stable than the seven-membered ring isomer. The chemical shift of the carbon
derived from CO2 was observed at 165.6 ppm. This resonance is shifted significantly downfield
compared to free carbon dioxide (125.7 ppm).230,231 The resonance for the bridging carbon
appears at 85.2 ppm, drastically upfield from the analogous carbon in dianionic species 3-5Tip
(129.4 ppm) and 3-6Tip (137.9 ppm). This confirms the rupture of the planarity in the system, as
the bridging carbon no longer participates in the conjugation of the π-electrons. Interestingly, the
insertion product did not show a signal in either the 11B or 10B NMR spectrum, despite numerous
attempts to detect them. However, MALDI-TOF mass spectrometry was used to confirm the
presence of the boron centers in the molecule. Figure 4-2 clearly shows that the isotopic
distribution observed in the spectrum matches the theoretical isotopic distribution of the
molecular formula.232,233
99
Tip
B
O
KO
OK
O
B
Figure 4-1 1H NMR spectrum of compound 4-1Tip (CD2Cl2, 600 MHz)
Figure 4-2 Truncated predicted isotopic distribution and MALDI-TOF spectrum of 4-1Tip
100
X-ray quality crystals were obtained by slow evaporation of a dichloromethane solution
of 4-1Tip, which confirmed the structure as the BINOL-analogue six-membered ring-expansion
product (Figure 4-3). The X-ray crystallographic analysis reveals a structure in which three
insertion product molecules assemble into a cluster bridged by six potassium ions (Figure 4-4).
The cluster also contains two molecules of THF coordinated to the potassium centers K1 and
K1’ (the solvent molecules are omitted in Figure 4-3 and Figure 4-4). The THF atoms were
disordered, but their positions were located from a difference Fourier map and were included in
the least squares refinements at fixed positions. The part of the structure of interest, excluding
the THF molecules, was free of disorder and the current analysis unequivocally establishes the
connectivity of the molecular structure of the compound as shown in Figure 4-3 and Figure 4-4.
The fused rings are planar, but the two-bridged rings are almost perpendicular with a dihedral
angle C3-C2-C2’-C3’ of 91.6(7)º. The boron center adopts a slightly distorted trigonal planar
geometry, with C-B-C angles close to the ideal 120º (see Table 4-1). The intraring B-C bond
length in 4-1Tip (1.506(9) Å) is shorter than the exocyclic B-C bond (1.574(8) Å), and it is also
shorter than the average B-C bond length found in Ph3B (1.577(6) Å)234. Furthermore, this bond
is very similar to the B=C bond found in 3-5Tip (1.504(3) Å), suggesting a higher bond order and
π-electron delocalization in the system. The pendant aryl ring is not coplanar with the fused rings
but is almost perpendicular with a torsion angle of –93.1(9)º. The C1-O2 bond distance is
considerably longer than the distance reported in products of carbon dioxide insertion into FLP
systems (1.2081(15) Å and 1.209(4) Å),235 consistent with a single bond character and a
carboxylate structure. The C1-C2 (1.373(7) Å) and C2-C2’ (1.494(7) Å) bond distances are
indicative of double and single bond character, respectively. The potassium centers are located
between the anionic oxygen atoms and the heteroacene ring of the other bridged fragment
101
(Figure 4-4). Therefore, the potassium centers are not only being stabilized by the anionic
oxygen centers, but also by π-electrons of the heteroacene rings.
C8 C3 C3'
C14
C9 C2 C2'
B1
C1
O1
O2
Figure 4-3 Thermal ellipsoid (50%) diagram of the molecular structure of 4-1Tip. Hydrogens,
potassium atoms and THF molecules have been removed for clarity

C9-B1 1.574(6) C8-B1-C9 123.9(6)
B1-C8 1.506(9) C9-B1-O1 118.6(6)
B1-O1 1.355(6) O1-B1-C8 117.6(6)
C1-O1 1.395(6) O1-C1-O2 113.2(4)
C1-O2 1.257(5) O1-C1-C2 118.7(4)
C1-C2 1.373(7) O2-C1-C2 128.0(5)
C3-C8 1.396(8) C3-C2-C2’-C3’ 91.6(7)
C2-C2’ 1.494(7) C14-C9-B1-C8 –93.1(9)
102
K3'
K2
K1 K1'
K3
K3''
K1'
K3'
K3
Figure 4-4 POV-ray depiction of 4-1Tip. Hydrogen atoms and THF molecules have been
removed for clarity. C: gray, B: orange, O: red, K: purple.
103
4.2.1 UV-Vis and florescence spectroscopy
In order to assess the photophysical properties of compound 4-1Tip, UV-Vis and
fluorescence spectroscopic analyses were performed in CH2Cl2 solution. The UV-Vis absorption
spectrum of compound 4-1Tip is shown in Figure 4-5 and shows only two broad bands at 300 and
400 nm, without any resolved vibrational transitions. Even though several basis sets and
functionals were used in order to perform TD-DFT calculations, the predicted UV-Vis did not
match the experimental one.§§ Most likely in solution the compound still forms a cluster,
changing the electronic properties of the compound in solution compared to the calculated
species. The emission spectrum shows a maximum at 455 nm (Figure 4-6).
0.7"
0.6"
Absorbance*/*a.*u.*
0.5"
0.4"
0.3"
0.2"
0.1"
0"
250" 300" 350" 400" 450" 500"
Wavelength*/*nm*
Figure 4-5 Absorption spectrum of compound 4-1Tip in CH2Cl2
§§
Calculations were performed using a single molecule, and not the cluster depicted in Figure 4-4.
104
Intensity(/(a.(u.(
400# 450# 500# 550# 600# 650# 700# 750#

Wavelength(/(nm(
Figure 4-6 Emission spectrum of compound 4-1Tip in CH2Cl2
4.2.2 Proposed mechanism of the carbon dioxide insertion
The fact that both compounds 3-5Tip and 3-6Tip gave the same CO2 insertion product was
surprising, but interesting from a mechanistic perspective. In order to explain this outcome, there
must be either an isomerization of 3-5Tip to 3-6Tip or an isomerization from 3-6Tip to 3-5Tip. Since
it was established in Chapter three that 3-5Tip is considerably higher in energy than the isomer 3-
6Tip, the isomerization of 3-6Tip to 3-5Tip seems to be very unlikely. Therefore, the isomerization
of 3-5Tip to 3-6Tip must be an early step in the mechanism and a proposed pathway is depicted in
Scheme 4-6. Starting from compound 3-5Tip, the carbonyl carbon of CO2 is attacked by the
nucleophilic bridged-carbon of 3-5Tip forming intermediate IA. In this case, the CO2 molecule is
essentially acting as a “big proton” during the rearrangement of the four-membered boracycle,
akin to the process observed in the proton-catalyzed rearrangement discussed in Chapter three.
The potassium centers are omitted in Scheme 4-6, but most likely they play a crucial role in the
105
stabilization of the CO2-inserted species. Carbon dioxide “activation” or reactivity invariably
involves both a Lewis base to attack the electrophilic carbon and a Lewis acid to attach and
stabilize the anionic oxygen.236-238 Nucleophilic attack on the borane by the electron rich
carbanion of the other borabenzocyclobutene induces ring opening to generate IB, positioning the
carbanion for attack on the other boron center to expand the remaining four membered ring,
giving IC. Subsequently, IC undergoes another attack by a second molecule of CO2 forming ID.
Consecutive nucleophilic attacks on the boron centers by the carboxylate anions, along with the
corresponding bond rearrangements (through intermediates IE and IF) leads to the formation of
the insertion product 4-1Tip. Likewise, starting from 3-6Tip the first CO2 insertion produces
intermediate IC, which would undergo the same processes described above to produce the same
insertion product as 3-5Tip.
106
O O
Tip C
O O Tip Tip
B CO2 C B B
B
B B
Tip
Tip Tip
3-5Tip IA IB
O Tip O Tip
O O O Tip
O Tip
Tip B B C B C
CO2 B CO2 B
C O B C B
O B
O Tip Tip IC
O ID Tip
IE
3-6Tip
The nucleophilic attack on the boron centers
might might be concerted
O O
O O
Tip B B Tip Tip B B Tip
O O
O O
IF
4-1Tip
Scheme 4-6 Proposed mechanism for the formation of 4-2Tip from 3-5Tip and 3-6Tip
4.3 Addition of carbon monoxide and characterization of insertion product
Addition of carbon monoxide to neutral compounds 2-4Tip and 2-5Tip only resulted in
decomposition of the starting materials. Decomposition of four-membered 2-4Tip was immediate
after addition of carbon monoxide producing an intractable mixture of compounds. The
decomposition of diborole 2-5Tip was more “clean”, after a few hours the starting material
completely disappeared and there was formation of at least three new products determined by 1H
NMR spectroscopy, but the identity of such species could not be determined.
107
Therefore, as in the case of carbon dioxide, we turned our attention to the direduced
boracycles 3-5Tip and 3-6Tip. Addition of carbon monoxide to compound 3-5Tip resulted in a
complex mixture of intractable products. However, diborole dianion 3-6Tip underwent a very
slow, but clean, reaction when a THF solution was sealed under one atmosphere of carbon
monoxide. At room temperature, the formation of the new species took four days, but at 70 ºC
the entire process took approximately 17 hours. The formation of the new species was
accompanied by a color change in the solution from red to dark blue and could be followed by
NMR spectroscopy (Figure 4-7). The NMR spectrum of compound 4-2Tip shows an asymmetric
structure suggesting that only mono insertion took place under the reaction conditions. Prolonged
heating (5 days, 70 ºC) did not change the appearance of the NMR spectrum. Therefore, the
reactivity of 3-6Tip towards carbon monoxide is quenched after the first insertion. Compound 4-
2Tip was isolated as dark blue brittle crystals in 65% yield after crystallization from THF and
hexanes.
THF
Tip KO
K Tip OK
B CO (1atm) B CO (1atm)
Tip
K B
B THF THF
B B
Tip K Tip
Tip OK
THF
3-6Tip 4-2Tip , 65%
108
3-6Tip + CO, 17 h
(4-2Tip)
3-6Tip + CO, 6 h
3-6Tip + CO, 0 h
Figure 4-7 Addition of carbon monoxide to 3-6Tip (70 ºC, THF-d8, 600 MHz)
The chemical shift of the boron centers was very difficult to find. In fact, after several
10
thousand scans only a single broad resonance centered at 46.6 ppm was observed in the B
NMR spectrum. Both resonances are likely overlapping in this signal. The carbon derived from
13
CO was found at 182.9 ppm by performing the insertion experiment using CO, shifted only
slightly upfield compared to free 13CO (184.9 ppm).
X-ray quality crystals were obtained by slow diffusion of hexanes into a THF solution of
4-2Tip (Figure 4-8). The molecule crystallizes as a dimer, where two potassium centers are
bringing the molecules (Figure 4-9). The bridging potassium atoms are solvated by one molecule
of THF each and the non-bridging potassium centers are solvated by two molecules of the
109
solvent. The B1-C1 bond distance is in agreement with previously reported B-C single
bonds.145,227,239 However, the B1-C8 (1.520(3) Å) bond distance is significantly longer than other
B=C bonds.39,74,183 In fact, the distance is of intermediate length between the B-C double bond
shown in 3-6Tip (1.479(4) Å) and the single bond in 2-5Tip (1.571(4) Å), and very similar to the
B-C bond shown in radical 3-4Tip (1.525(4) Å). Likewise, the C8-C7 (1.449(2) Å) bond distance
is slightly shorter than the distance observed in 3-6Tip (1.466(3) Å), and the C7-C15 (1.414(3) Å)
bond distance is significantly longer than the C-C double bond in 2-5Tip (1.367(5) Å). This data
suggests that the B1-C8 double bond in 4-2Tip is more delocalized into the π-system than the
double bond in 3-6Tip. The exocyclic B-C distances are similar to those reported in other
boracyclic compounds,80,83,239,240 for example 9-phenyl-9-borataanthracene (1.582(3) Å).183 The
C15-B2-C14 angle (118.7(2)º) is significantly larger than the C1-B1-C8 (103.9(2)º) angle due to
the release of angle strain by the expansion from a 5- to a 6-membered ring. One of the
potassium centers is 𝜂4-coordinated to the six-membered heterocycle, which can be seen in the
difference between the K1-C8 and K1-B1 bond distances (2.870(2) and 3.467(2) Å respectively).
The other potassium center is coordinated to the anionic oxygen O1 with a distance of 2.614(2)
Å, but also stabilized by an 𝜂6-coordintion to the B-aryl ring. The distance of this cation-π
interaction241,242 is 3.024(3) Å, similar to those reported in other complexes with potassium-π
interactions.126,243
110
C14
C9
B2
C16 C8 K1
C15
B1
C7
K2
C1 O1
C6
Bond Distances (Å) Bond Distances (Å)

C16-B1 1.587(2) C15-O1 1.317(2)
B1-C8 1.520(3) O1-K2 2.614(2)
B1-C1 1.570(2) C8-K1 2.870(2)
C1-C6 1.423(3) Bond Angles (º)
C7-C8 1.449(2) C8-B1-C1 103.9(2)
C8-C9 1.442(2) C15-B2-C14 118.7(2)
C14-B1 1.521(3) C1-B1-C16-C17 –70.1(3)
B1-C15 1.553(3) C14-B2-C31-C32 –98.9(2)
111
Figure 4-9 POV-ray depiction of 4-2Tip. Hydrogen atoms have been removed for clarity. C:
gray, B: orange, O: red, K: purple.
4.3.1 4.4 UV-Vis and fluorescence spectroscopy
The UV-Vis absorption spectrum of compound 4-2Tip recorded in THF is shown in
Figure 4-10. The spectrum exhibits two maxima of similar intensity centered at 581 and 355 nm.
Interestingly, clear vibrational transitions are observed in the longer wavelength region. The
longest absorption maximum was attributed to a HOMO-LUMO transition based on TD-DFT
calculations (B3LYP/6-311G(d)) and was assigned as a S0 à S1 transition. The vibrational
transitions were observed at 543, 581 and 625 nm, and the separation between these peaks was
1204 cm-1 and 1211 cm-1.
112
1"
0.9"
0.8"
0.7"
Absorbance*/*a.*u.*
0.6"
0.5"
0.4"
0.3"
0.2"
0.1"
0"
300" 350" 400" 450" 500" 550" 600" 650" 700"
Wavelength*/*nm*
Figure 4-10 Absorption spectrum of compound 4-2Tip in THF
This type of vibrational transition is common for rigid aromatic systems86 and is often
apparent in larger acenes.38,244,245 For instance, in naphthalene and pentacene the vibrational
spacing between the three longest absorptions are 1092 cm-1, 1472 cm-1, 1393 cm-1 and 1474 cm-
1
, 1283 cm-1, 1424 cm-1 respectively.38,246 Furthermore, similar vibrational spacing has been
reported for boraacenes.38 The maxima of the four longest wavelength absorptions of 6-
borapentacene are 668 nm, 723 nm, 799 nm, and 891 nm which are separated by 1191 cm-1,
1276 cm-1, and 1288 cm-1, respectively.38 All these vibrations fall in the range associated with C-
X (X = C, H) IR stretching and bending transitions.247-249
The Jablonski diagram (Figure 4-11) can be used to explain the origin of these vibrational
transitions. In a very simplified situation, when a chromophore absorbs light all the energy
possessed by a photon is transferred to the chromophore. This promotes an electronic transition
from the ground state S0 to the excited stated S1. If the absorbed energy is greater than that
113
required to precisely produce the transition from S0 to the lowest energy level of S1, the molecule
will also undergo changes in vibration and/or rotation, or even transition to a higher electronic
state such as S2.250-252 The vibrational transitions observed in compound 4-2Tip are from the
lowest vibrational ground state (0) to an excited vibrational state in S1. The longest wavelength
of absorption corresponds to a 0-0 transition, with each successive maximum in the absorption
spectrum representing a higher vibrational level in S1. Therefore, the transition observed at 625
nm corresponds to a 0-0 transition and the ones at 581 and 543 nm to 0-1 and 0-2, respectively.
Figure 4-11 Jablonski diagram showing absorption and emission of photons. Reprinted by
permission from Macmillan Publishers Ltd: Nat. Methods 2005, 2, 910, copyright 2005
Compound 4-2Tip is dark blue in solution and shows purple emission under UV light. As
in its absorption profile, the emission profile of 4-2Tip also exhibited vibrational transitions
(Figure 4-12). The maxima of the two emissions are 648 and 692 nm, which are separated by
114
981 cm-1. The Jablonski diagram in Figure 4-11 can also be used to explain the vibrational
transitions in the emission spectrum. After excitation, the molecule uses several pathways to
return to the ground state. According to Kasha’s rule, as a result of internal conversion, emission
of a photon occurs from the lowest excited state (S1).253 From the lowest vibrational state of S1
the molecule can undergo transitions to several vibrational levels of S0, resulting in the
observation of the vibrational levels in the emission profile.250-253

Intensity(/(a.(u.(
590$ 640$ 690$ 740$ 790$ 840$

Wavelength(/(nm(
Figure 4-12 Emission spectrum of compound 4-2Tip in THF
4.3.2 Molecular Orbital (MO) Calculations
The UV-Vis spectrum of compound 4-2Tip revealed some vibrational information. To
gain further insight into the electronic structure of 4-2Tip, the ground state structure was
115
investigated computationally. Figure 4-13 shows the HOMO and LUMO orbitals of 4-2Tip. From
the diagrams shown below it can be seen that the HOMO is π in nature, with the main framework
supporting the majority of the MO. There is no contribution from the B-aryl ring, which is in
agreement with its orthogonal position relative to the main framework. The LUMO shows a
large contribution from the main framework and a small contribution from the B-aryl ring. With
these MOs in mind it is not surprising that the vibrational modes of the molecules were revealed
in their absorption spectra.
HOMO LUMO
Figure 4-13 Calculated HOMO (left) and LUMO (right) of 4-2Tip (B3LYP/6- 311G(d))
4.3.3 Proposed mechanism of the carbon monoxide insertion
It is possible to draw three resonance structures for carbon monoxide as shown in Scheme
4-8.254 Although resonance structure (i) has formal charges, and the positive charge is on the
116
more electronegative atom (oxygen vs carbon), all atoms of structure (i) have complete octets,
making this structure very stable. The double-bonded structure (ii) has no formal charges and the
singly-bonded structure (iii) has a formal positive charge on carbon and a negative charge on
oxygen (in agreement with the atomic electronegativities). Even though the value of the dipole
moment of carbon monoxide (0.112 D)255 is very low (suggesting equal contributions from
structure (i) and (iii)), its direction corresponds to a positive charge on the oxygen atom,256
implying a higher contribution from resonance structure (i). Furthermore, the bond length
between the carbon atom and the oxygen atom is 1.128 Å,257 consistent with a carbon-oxygen
triple bond. This is also in agreement with the observed classical reactivity of carbon monoxide,
where the carbonyl center acts as a nucleophile. In order to explain the insertion of carbon
monoxide into 3-6Tip we have proposed two mechanisms taking into account the contributing
resonance structures.
The first mechanism invokes the electrophilicity of the carbonyl carbon indicated in the
resonance structure (iii) (A, Scheme 4-8). The nucleophilic bridged-carbon in 3-6Tip might
interact with carbon monoxide forming the carbene intermediate IA. The σ-electron-withdrawing
oxygen, along with its π-electron-donating capabilities, favours a singlet ground-state
multiplicity.258,259 An attack of this carbene on the electrophilic boron center forms a three-
membered boracycle (intermediate IB). A bond rearrangement from this intermediate releases the
strain of the three-membered cycle, forming the more stable six-membered ring product. Clearly,
(based on the experimental evidence that supports a higher contribution from resonance structure
(i)) carbon monoxide should be considered a very week electrophile. Therefore, the formation of
IA is very unlikely, which explains the extremely slow reactivity of the system at room
temperature. X-ray parameters support the lack of reactivity towards the second insertion. X-ray
117
crystallographic analysis showed that 4-2Tip displays a high degree of delocalization of the π-
electrons in the core of the molecule (vide supra). This might decrease the nucleophilic character
of the other bridged-carbon center, hampering its nucleophilic attack to carbon monoxide and
suppressing the reactivity completely; consequently, only mono-insertion is observed.
C O C O C O
(i) (ii) (iii)
A
Tip Tip Tip Tip
B CO B B B
B B B B C
C C Tip
Tip C Tip Tip
O O O 4-2Tip
IA IB O
3-6Tip
B
Tip Tip Tip Tip
B B B
CO B
B B B B C
Tip C C Tip
Tip Tip
C O ID O O 4-2Tip
IC
3-6Tip O
Scheme 4-8 Plausible mechanisms for the formation of 4-2Tip
The second mechanism (B, Scheme 4-8) takes advantage of resonance structure (i), and is
more in agreement with the traditional reactivity of carbon monoxide. Based on the reactivity of
dianionic diborole 3-6Tip towards protons and carbon dioxide, the electron density of the B=C
bond is more localized on the carbon center. This allows for interaction of the nucleophilic
carbon of carbon monoxide and the boron center forming intermediate IC. A nucleophilic attack
on the carbonyl carbon takes place, forming intermediate ID. Finally, a bond rearrangement from
this intermediate releases the strain of the three-membered cycle, forming the more stable six-
118
membered ring product. Even though this mechanism makes more sense with the traditional
reactivity of carbon monoxide, it does not help to explain the lack of formation of the double-
insertion product. As mentioned before, based on X-ray crystallographic analysis the π-system is
more delocalized, which should make the interaction of the boron center and the carbonyl carbon
more feasible, favoring the second insertion of carbon monoxide. However, the experimental
data shows that the double-insertion product is not formed even at prolonged reaction times or
higher temperatures.
This chapter described the ring-expansion of the borole fragment in compounds 3-5Tip and
3-6Tip using carbon monoxide and carbon dioxide. Surprisingly, the insertion of carbon dioxide
into 3-5Tip and 3-6Tip produced the same product 4-1Tip. After the first electrophilic attack of
carbon dioxide to 3-5Tip the new species undergoes an isomerization similar to the one reported
for the electrophilic attack of a proton to 3-5Tip. This explains the formation of the
thermodynamically more stable product 4-1Tip from 3-5Tip and 3-6Tip (Scheme 4-6). In the solid
state compound 4-1Tip assembles into a cluster with a structure similar to 1,1'-bi-2-naphthol
(BINOL), which is a ligand commonly used for transition-metal catalysed asymmetric
synthesis.260-262 Addition of carbon monoxide to 3-6Tip slowly produced the insertion product 4-
2Tip. Compound 4-2Tip shows a red shift in the absorption and emission spectra compared to the
starting material 3-6Tip.
119
Chapter Five: Conclusions and future work
5.1 Conclusions
Chapter two of this thesis dealt with the routes and challenges to prepare the target
compound benzoborole-fused benzoborole 2-5Tip. In the quest to accomplish the goal, the
boracyclobutylidene compound 2-4Tip was isolated as a yellow solid. Compound 2-4Tip is an
isomer of the desired boracycle and can actually be converted to 2-5Tip by a light-driven
photoisomerization. Although compound 2-5Tip has 14 π-electrons and might be considered
aromatic, the five-membered borole rings still hold antiaromatic character.
While small quantities of pure 2-5Tip can be isolated by the photochemical isomerization,
attempts to garner workable amounts of 2-5Tip on a preparative scale using this procedure were
hampered by low efficiency. Chapter three focused on finding a route to thermally access
benzoborole-fused benzoborole 2-5Tip. In that chapter the electrochemistry of compounds 2-4Tip
and 2-5Tip was explored in detail. Radical anions 3-2Tip, 3-3Tip and 3-4Tip were formed upon one-
electron reduction. These compounds were isolated and characterized. In the case of 3-4Tip, an
X-ray structural determination was possible, allowing for a detailed analysis of the bond length
changes. The direduced species 3-5Tip and 3-6Tip were formed upon reduction using potassium
naphthalenide. Compound 3-5Tip underwent an acid-catalyzed isomerization to form 3-6Tip. It
was found that t-BuOH was the best reagent for inducing this skeletal rearrangement. Finally,
boracycle 3-6Tip underwent oxidation using silver triflate and this provided a thermal route to the
synthesis of 2-5Tip.
120
Chapter four focused on the reactivity studies of the boracycles reported in chapters two
and three towards carbon monoxide and carbon dioxide. Neutral compounds 2-4Tip and 2-5Tip
showed no reactivity or decomposition. However, the dianionic species 3-5Tip and 3-6Tip readily
reacted with carbon dioxide. Interestingly, both compounds formed the same insertion product 4-
1Tip. Compound 3-5Tip decomposed with carbon monoxide, but compound 3-6Tip slowly
produced the insertion product 4-2Tip.
Overall, this thesis has provided new pathways to synthesize novel boron-containing
heterocycles and has also explored the reactivity of those molecules. Furthermore, this
dissertation has contributed to expanding the knowledge about aromatic and antiaromatic
systems. In particular, the effect of heteroacenes fused to the borole ring was explored,
complementing the work reported by Yamaguchi.
CO2
THF THF
Tip Tip KO
K K
B B CO2 O
t-BuOH
Tip B B Tip
B
B O
Tip K
Tip K 3-6Tip OK
THF 3-5Tip
THF
CO 4-1Tip
AgOTf 2 eq. KNaph
2 eq. KNaph
Tip KO
Tip Tip
B B
B 254 nm K
B B B
Tip Tip Tip
2-4Tip 4-2Tip
2-5Tip
Scheme 5-1 Graphical Thesis Summary
121
5.2 Future Work
The work described in this thesis has also opened the door for new areas of research. In the
following subsection a research proposal will be described in detail, followed by two small
research ideas.
5.2.1 Intermetallic Communication in Organometallic Complexes
The “boom” of organometallic chemistry was marked in the early 1950’s when Pauson,
erroneously, published ferrocene as a newly discovered sigma complex.263 Upon observation of
the structure, Wilkinson realized that it was incorrect and proposed the structure of ferrocene to
be an 18-electron sandwich-type complex.264 Subsequently, several other sandwich-type
complexes were reported using different transition metals. Nowadays, there are sandwich-type
complexes of almost every transition metal in the periodic table.265 Geoffrey Wilkinson and
Ernest Otto Fischer eventually received the Nobel Prize in Chemistry "for their pioneering work,
performed independently, on the chemistry of the organometallic, so called sandwich
compounds".
A great deal of research has been focused on the synthesis and properties of one-
dimensional organometallic sandwich type complexes as the one in Figure 5-1, due to their
potential application as advanced materials.266,267 The possibility of a high degree of electronic
communication between the transition metals in an odd-electronic system, associated with the
electron delocalization and electronic cooperative interactions mediated by their ligands, might
offer new materials with interesting electrical and/or magnetic properties.268,269 Undoubtedly,
122
bimetallic sandwich complexes are the perfect scaffolds to study such electronic interactions as
they can be envisioned to be subunits of a potential one-dimensional conducting material.270-273
M M M
n
Figure 5-1 Organometallic polymer
Since the degree of communication is primarily controlled by the bridging ligand, to
promote an effective communication between the metal centers, the ligand must provide an
effective electronic coupling pathway. Therefore, compounds exhibiting conjugated systems
appear as the best candidates to promote such electronic communication through their π-
orbitals.268
The electron-transfer in bimetallic compounds is commonly studied using mixed-valence
systems as models. A mixed-valence system is generated when an electron is removed from a
polynuclear molecule. There are two extreme situations based on the Robin and Day’s rule: class
1 and 3.264
- Class 1: the two redox centers have a different environment and the valence is localized
whatever the time scale (usually referred to as average-valence complexes).
- Class 2: the two redox centers have identical environments, but the valence is localized
at the infrared time scale (10–13 s).
- Class 3: the valence is delocalized on the infrared time scale (10–13 s).
123
Figure 5-2 Classification of mixed-valence systems according to Robin and Day’s rule
Pentalene, which might be considered as the bicyclic homologue of cyclopentadiene, is a
reactive antiaromatic polycyclic hydrocarbon that can be deprotonated twice to form a more
stable 10 π-electron aromatic salt. The aromatic system has been studied extensively as a
bridging ligand in mixed-valence systems.270,273 It has been shown that this polycyclic
hydrocarbon ligand is excellent at facilitating the intermetallic communication between metals;
the extent of the electronic delocalization has been probed by a variety of experimental
techniques, such as Mossbauer spectroscopy, cyclic voltammetry, and X-ray crystallography.
Other systems using indenyl, asymmetric indacenyl and symmetric indacenyl as the bridging
ligand, have also been studied, although in less detail.268,274,275
10 π-electrons 14 π-electrons + 2+
Fe Fe Fe
2-
pentalenyl s-indacenyl Fe Fe Fe
Aromatic Ligands
Scheme 5-2 Aromatic ligands and some iron bimetallic complexes
124
Several homo and hetero bimetallic systems using pentalenyl ligand have been prepared,
which include Fe-Fe, Co-Co, Ni-Ni, Ru-Ru, Fe-Ru, Fe-Co and their one and two electron
oxidized derivatives.270,273,276,277 The results of the experiments showed that mixed-valence
system with metals belonging to the same group display strong electron coupling between the
metal sites (class 3).
All of the π-systems used to investigate the electronic communication of bimetallic
complexes are aromatic and only contain carbon atoms. However, isolation of complex 3-6Tip
(16 π-electrons) allows the study of bimetallic communication in antiaromatic π-systems for the
first time. Furthermore it allows for the study of the communication when the bridging ligand is
a heteroacene ring.
THF
Tip Tip
K M
B B
2 +
M B THF B
acac M
Tip K 3-6Tip Tip
M=Fe, Co, Ni
THF
Scheme 5-3 Proposed synthesis of bimetallic systems containing the benzoborole-fused

benzoborole framework
It would be attractive to synthesize and characterize homo bimetallic species using the
first-row transition metals Fe, Co, and Ni. Of particular interest would be the study of the degree
electronic communication between the metals. The synthesis of the sandwich complexes could
be carried out in a similar way as the pentalenyl derivatives were prepared.270 Cp*M(acac)
(acac=acetylacetonate) complexes have been shown to be excellent precursors for these types of
compounds and are relatively easy to synthesize.278 Scheme 5-3 only shows the synthesis of
125
homobimetallic derivatives, but the synthesis of the heterobimetallic derivatives could be
performed in a similar fashion, with the first step being the addition of one equivalent of
Cp*M(acac) to the ligand, followed by the addition of another equivalent of a different
Cp*M’(acac). The synthesis of mixed-valence complexes could be achieved by the reaction of
the neutral transition metal complexes with an oxidizing agent such as ferrocenuim
tetrafluoroborate. Of course, the oxidizing agent must be chosen based on cyclic voltammetry
experiments performed on the neutral species.
The work proposed in this subchapter would provide further insight into the intermetallic
communication between metal centers that are separated through an antiaromatic π-conjugated
ligand. Furthermore, it could provide a feasible pathway to the synthesis of conducting
organometallic polymers.
5.2.2 Development of new boron-containing heterocycles
Polycyclic aromatic hydrocarbons, generally referred to as “acenes”, have garnered
considerable interest in materials research.1,4 They are attractive because they are planar
molecules that possess an extended π-conjugated system which leads to exceptional
photophysical and electrochemical properties including intense luminescence and high charge
carrier mobility.279-281 Undoubtedly the most studied member in the family of acenes is
pentacene. Pentacene has been in the eyes of researchers for a long time due to its superior
charge transport qualities.282 Its ability to function as an organic p-type semiconductor has
allowed it to be used in materials such as thin film transistors and organic solar cells.283,284
126
Indenofluorene is another polycyclic aromatic hydrocarbon that has been heavily studied
in the last couple of years, mainly by the group led by Professor Michael Haley.285-287
Indenofluorene closely resembles pentacene, but the former is formally classified as an
antiaromatic molecule (20 π-electrons). This group has extensively studied the photophysical and
electrochemical properties of several indenofluorene derivatives. In fact, they utilized an
indenofluorene derivative as the active element in a single-crystal OFET that exhibited
ambipolar behaviour with Au source/drain contacts.288
It would be interesting to prepare borataindenofluorene derivatives such as V-2Ar in order
to study their properties (Scheme 5-5). The precursor V-1Ph was reported in a patent several
years ago,289 but interestingly, according to the authors, the compound is air and moisture stable.
This is very rare given the tendency for B-C bonds to undergo protic cleavage.137 Compound V-
1Ph was prepared by lithiation of the tetrabrominated terphenyl precursor, followed by quenching
with dichlorophenylborane and an acidic workup (Scheme 5-4).
Ph
Br Br B
1) 4 eq. s-BuLi
2) 2 eq. PhBCl2
B
Br Br
Ph V-1Ph
Scheme 5-4 Synthetic route reported for V-1Ph
The strategy reported in the patent could be followed in order to isolate the phenyl
derivative. If the strategy described in the patent does not lead to clean formation of V-1Ph the
strategy presented in Scheme 5-5 could be used as a possible alternative. Furthermore, the latter
strategy would also allow for the incorporation of bulkier substituents on boron. All of the steps
127
presented in Scheme 5-5 are well known and no potential pitfalls in this endeavour are foreseen.
After isolation of compounds V-1Ar, reduction would be performed using strong reducing agents
such as potassium naphthalenide or potassium graphite. If compounds V-2Ar can be isolated, a
complete study of their photophysical and electrochemical properties could be performed. Even
though the dearomatization produced by the addition of two electrons to V-1Ar might be
considered a destabilizing effect, this process has been observed in transition metal catalysis with
cooperative ligands.290,291
Cl
Br Br Sn B
1) 8 eq. t-BuLi BCl3
2) 2 eq. Me2SnCl2
Sn B
Br Br
Cl
CuAr
Ar Ar
B B
2 e–
B B
Ar = Ph, V-2Ph Ar Ar = Ph, V-1Ph
Ar
Ar = Tip, V-2Tip Ar = Tip, V-1Tip
Scheme 5-5 Proposed synthetic route to borataindenofluorene derivatives
5.2.3 BoraBINOL complexes
1,1'-Bi-2-naphthol (BINOL) has been extensively used in asymmetric catalysis in a broad
spectrum of transformations.292 BINOL has been shown to form very enantioselective catalysts
with main group elements,293,294 transition metals,293 f-block elements,295 and heterobimetallic
combinations296 from these groups.
128
KO HO
O
Tip B B Tip
O
OK OH
4-1Tip BINOL
Figure 5-3 4-1Tip and BINOL compounds
Since compound 4-1Tip could be considered an equivalent of a binolate ligand, it would
be interesting to explore the chemistry of 4-1Tip as a ligand for transition metals or main group
elements. Since compound 4-1Tip is already anionic, salt metathesis could be used to install the
ligand into halogenated metal complexes. Another possibility would be to prepare
heterobimetallic multifunctional catalyst using lanthanum296,297 or cerium,298,299 such as the
complexes shown in Figure 5-4. For instance, compounds like the ones shown in Figure 5-4 were
prepared using cerium(III) tris(trifluoromethanesulfonate) and the corresponding alkali metal salt
of the binolate ligand by salt metatesis.299
M = Li, Na, K
O O
M M
Ce
O O
O O
M
Figure 5-4 Heterobimetallic multifunctional catalyst using cerium299
129
The projects described in this chapter would complement the chemistry presented in this
thesis. In particular, the first proposal is very interesting form a fundamental point of view
because the use of antiaromatic compounds as bridging ligands has never been explored before.
Furthermore, this ligand might be the key to access an elusive highly conductive organometallic
polymer.
130
Chapter Six: Experimental details
6.1 General Considerations
6.1.1 Laboratory Equipment
Storage and manipulation of all oxygen and moisture sensitive compounds was performed
under an argon atmosphere in an Innovative Technology System One, or Vac Atmospheres glove
box. All reactions were performed on a double manifold vacuum line following standard
procedures.300 Passage of argon through an OxisorBW scrubber (Matheson Gas Products)
removed any residual oxygen and moisture. Controlled addition of gases was achieved through
use of needle valves on swage lock stainless steel or Tygon plumbing; while vacuum and
glassware were sealed with Kontes Teflon taps on ground glass joints. Standard swivel frit
apparatus was employed for all air sensitive filtrations. Prior to each reaction, all glassware was
heated to 110 °C for a minimum of two hours, followed by immediate vacuum pump down in the
glove box anti-chamber or on the vacuum line.
6.1.2 Solvents
Toluene, hexane and tetrahydrofuran (THF) solvents were dried and purified using the
Grubbs/Dow purification system301 and stored in 500 mL thick-walled glass vessels under
vacuum over sodium/benzophenone ketal. Pentanes were dried over CH2Cl2 and stored over
sodium/benzophenone ketal in thick-walled glass vessels under vacuum. Dichloromethane were

131
dried over CH2Cl2 and stored over molecular sieves (4A) in thick-walled glass vessels under
vacuum. 4A molecular sieves purchased from Aldrich were “activated” by rinsing with
dichloromethane prior to heating to 160 °C to 180 °C at 10-3 torr for 12 hours and stored in the
glove box. Unless otherwise noted, solvents were introduced into the reaction vessels via
vacuum distillation with condensation at –78 ºC. Deuterated solvents including benzene-d6,
dichloromethane-d2, and toluene-d8 were dried over activated sieves and stored under vacuum.
Tetrahydrofuran-d8 was dried over sodium/benzophenone ketal and stored under vacuum.
6.1.3 Instrumentation
Nuclear magnetic resonance spectroscopy (1H, 11

B, 13
C{1H}, HSQC, HMBC, and COSY
experiments) was performed on Bruker 400 MHz (1H: 400 MHz; 11B: 128 MHz, 13C: 100 MHz)
or Bruker 600 MHz (1H: 600 MHz; 11B: 192 MHz, 13C: 150 MHz) spectrometers. All 2D NMR
experiments were performed using Bruker 400 MHz or Bruker 600 MHz spectrometers. All 1H
NMR spectra were referenced to SiMe4 through residual 1H resonance(s) of the employed
11
solvent: CD2Cl2 (5.32 ppm) or THF-d8 (3.58 ppm). B NMR spectra were referenced to an
external standard of boron trifluoride diethyl etherate (0.0 ppm) in C6D6 prior to spectrum
acquisition. 13C{1H} NMR spectra were referenced relative to SiMe4 through the resonance(s) of
the employed solvent: CD2Cl2 (54.0 ppm) or THF-d8 (25.31 ppm). NMR spectra were processed
and analyzed with MestReNova (v8.0.0-5850) NMR software. 1H NMR spectra are represented
in the following format: chemical shift in ppm (multiplicity, coupling constant in Hz, number of
protons). 11B and 13C{1H} spectra are represented in the following format: chemical shift in ppm.
132
13
Absolute assignments of C{1H} resonances was achieved through HSQC and HMBC
correlation experiments.
X-Ray crystallography was carried out on either a Nonius Kappa CCD diffractometer
using graphite-monochromated Mo Kα radiation or a Bruker Smart APEX II three-circle
diffractometer using Cu Kα radiation. X-ray crystallographic analyses were performed by Dr.
Masood Parvez (University of Calgary) or Dr. Mike Sgro (Piers Group). More details on
individual structures may be found in Appendix A. UV-Vis spectra were obtained on a Varian
Carey 5000 UV-Vis-NIR spectrophotometer operating in single-beam mode. Fluorescence
spectra were obtained on a Horiba Jobin Yvon FluoroMax-4. Steadystate emission spectra were
obtained at room temperature using an Edinburgh Instruments FLS920 spectrometer equipped
with a Xe900 450W steady state xenon arc lamp, TMS300-X excitation monochromator,
TMS300-M emission monochromator, Hamamatsu R2658P PMT detector and corrected for
detector response. Infrared spectra were obtained on a Nicolet Avatar IR spectrophotometer.
Elemental analyses (C, H, N) were performed by Mr. Jianjun Li on a Perkin-Elmer Model 2400
series II analyzer. High-resolution mass spectra were obtained by Mrs. Dorothy Fox on a Kratos
MS-80 spectrometer via electron impact (EI), by Mr. Wade White (direct ESI-MS) on samples
prepared in the glove box in a gas tight syringe or by Mrs. Qiao Wu on a Bruker Autoflex III
using MALDI-TOF with a Smartbeam laser system. EPR measurements were made on a Bruker
EMX10/12, equipped with VT capabilities.
Calculations were conducted using the Gaussian 09 program. Whenever possible input
geometries were derived from X-ray data in the form of .pdb files. Building or modification of
input files was conducted on Gauss View. All structures were optimized until frequency
calculations gave only positive values and then used for TD-DFT and NICS calculations.
133
Computational details are reported as method/basis set and optimized x,y,z coordinates are
shown in Appendix B. Molecular orbital surfaces were generated using the cube generator on
Gaussian 09 with fine grid and an iso-value of 0.03.
6.1.4 Starting Materials
Trimethyl tin chloride was purchased from Alfa Aesar; bis(pentamethylcyclopentadienyl)
cobalt(II), silver trifluoromethanesulfonate, 4-methoxyphenol, bis(trifluoromethane)sulfonamide,
2,6-dimethylphenol, t-butanol, bis(triphenylphosphoranylidene)ammonium chloride, copper
bromide and BCl3 (1M solution in heptane), nBuLi (1.6 M in hexanes), tBuLi (1.7 M in
heptanes), carbon monoxide and 13CO (99% 13C) were purchased from Sigma-Aldrich; 1-bromo-
2-iodobenzene, 2-bromo-1,3,5-triisopropylbenzene were purchased from TCI America. 2,2'-
dibromodiphenylacetylene,27 2,4,6-tri-isopropylphenyl copper,114 2,4,6-tri-methylphenyl
cooper,113,302 potassium graphite124 prepared according to literature procedures. Carbon dioxide,
bone-dry grade 3.0, and 13CO2 (99% 13C) were obtained from Praxair and Cambridge Isotopes,
respectively, and used as received.
134
6.2 Experimental Details for Chapter 2
6.2.1 Synthetic Procedures
Synthesis of 2-1
Me3Sn
SnMe3
t-BuLi (1.7 M in heptanes, 21.0 mL, 35.7 mmol) was slowly added to a solution of 2,2’-
dibromophenyl acetylene (3.00 g, 8.93 mmol) in THF (100 mL) at –78 ºC. After stirring for 60
minutes at –78 ºC, a solution of trimethyltin chloride (3.737g, 18.8 mmol) in THF (50 mL) was
added drop-wise, after which the solution turned colourless. The solution was allowed to
gradually warm to room temperature over 16 hours, at which time the solvent was removed in
vacuo to yield 2-1 (3.030 g, 83%) as an off-white solid. The crude product can be used directly
in the next step or purified by chromatography column using hexanes as eluent. 1H NMR
(CDCl3): δ 7.55 – 7.46 (m, 4H), 7.35 – 7.29 (m, 4H), 0.40 (s, 18H). 13C{1H} NMR (CDCl3): δ
146.19, 135.86, 131.43, 130.75, 128.53, 127.62, 92.19, –8.68. HRMS: Calcd for C19H23Sn2
([M]+-CH3): 488.9838, Observed: 488.9837.
135
Synthesis of 2-2
Cl
Cl B
B Cl
Cl
BCl3 (1.0 M in heptanes, 18 mL, 18 mmol) was added to a solution of 2-1 (3.00 g, 5.95 mmol) in
toluene (40 mL) at -78 ºC. The solution was stirred at room temperature for 16 hours. After this
period of time, the solution turned from clear/colourless to an orange colour. Solvent and
SnMe3Cl were removed in vacuo at 40 ºC for 6 hours (caution when disposing the traps
containing SnMe3Cl!). Hexanes were transferred (30 mL), the suspension was cooled down to –
78 ºC for 20 min and filtered in cold to yield 2-2 (2.505 g, 90%) as an orange solid. 1H NMR
(CDCl3): δ 8.09 (ddd, J = 7.5, 1.3, 0.7 Hz, 2H), 7.75 – 7.66 (m, 2H), 7.59 (td, J = 7.6, 1.4 Hz,
13
2H), 7.44 (td, J = 7.6, 1.3 Hz, 2H). C{1H} NMR (CDCl3): δ 137.40, 133.85, 133.62, 128.99,
127.99, 95.34 (the carbon atoms bonded to the boron centers were not observed due to
11
quadrupolar relaxation). B NMR (CDCl3): δ 55.5. HRMS: Calcd for C14H8B2Cl4 ([M]+):
339.9537, Observed: 339.9727.
Synthesis of 2,4,6-tri-isopropylphenyl copper
Cu
Although not discussed in Chapter two, an improved synthesis of 2,4,6-tri-isopropylphenyl
copper114 was developed during the current work, adapted from by work published by Koten.114
In a two-neck round-bottom flask 2-bromo-1,3,5-triisopropylbenzene (6.00 g) was dissolved in
136
ether (40 mL). At –78 ºC t-BuLi (25 mL, 1.7 M) was added slowly and the solution was warmed
to room temperature and stirred for 2 h. In a 150 mL round-bottom flask CuBr (3.130g) was
suspended in ether (40 mL) and at –78ºC TipLi was added slowly and the solution was stirred for
2 h at room temperature. Solvent was evaporated and the round-bottom flask was connected to a
swivel frit apparatus with another 150 mL round-bottom flask. The solid was dissolved in
hexanes and filtered when warm (filtration must be done slowly!). The solid in the frit was
washed once and solvent was removed. The off-white solid was transferred into a 50 mL round-
bottom flask and using, pentanes (25 mL) were transferred and the solution was stirred for 30
min at –78ºC. Solution was filtered in cold, giving a white solid (3.781 g, 63% yield). The
spectroscopic data are consistent with previously published data.114
Synthesis of 2-3Ph
Ph
Cl B
B Cl
Ph
Toluene (25 mL) was transferred into an evacuated flask containing 2-1 (1.000 g, 1.98 mmol). A
solution of chlorophenylborane (0.692 g, 4.37 mmol) in toluene (10 mL) was added at –78 °C.
The resulting mixture was stirred at room temperature for 16 h. The mixture was filtered at that
temperature and the solvent was removed in vacuo. Hexanes were transferred and the suspension
was filtered at room temperature to yield 2-3Ph (0.472 g) as an off-white solid in 56%. 1H NMR
(CDCl3) δ 8.05 – 7.94 (dd, J = 8.1, 1.4 Hz, 2H), 7.62 – 7.54 (m, 1H), 7.54 – 7.47 (m, 1H), 7.47 –
13
7.39 (m, 2zzH), 7.37 – 7.28 (m, 1H), 6.97 – 6.82 (m, 1H). C{1H} NMR (CDCl3): δ 142.51,
137
138.08, 137.60, 134.07, 133.33, 132.21, 130.26, 127.96, 127.49, 126.11, 94.52, 77.16. 11B NMR
(CDCl3): δ 63.4. HRMS: Calcd for C26H18B2Cl2 ([M]+): 422.0972, Observed: 422.0975.
Synthesis of 2-3Mes
Mes
Cl B
B Cl
Mes
Toluene (50 mL) was transferred into an evacuated flask containing 2-2 (0.500 g, 1.47 mmol)
and CuMes (0.592 g, 2.94 mmol) at –78 °C. The resulting mixture was stirred at 65 °C for 16 h.
After this period of time, the solution turned yellow with a white solid in suspension. The
mixture was filtered at that temperature and the solvent was removed in vacuo. Hexanes were
transferred and the suspension was filtered at room temperature to yield 2-3Mes (0.625 g) as a
yellow solid in 84%. 1H NMR (CDCl3) δ 8.02 (dd, J = 7.6, 1.5 Hz, 2H), 7.43 (td, J = 7.5, 1.6 Hz,
2H), 7.36 (td, J = 7.5, 1.4 Hz, 2H), 6.99 (dd, J = 7.7, 1.3 Hz, 2H), 6.77 (s, 2H), 2.21 (s, 6H), 2.19
13
(s, 12H). C{1H} NMR (CDCl3) δ 138.62, 137.84, 137.57, 134.53, 132.89, 130.17, 127.84,
127.73, 94.88, 22.38, 21.29 (the carbon atoms bonded to the boron centers were not observed
due to quadrupolar relaxation). 11B NMR (CDCl3): δ 68.4. HRMS: Calcd for C32H30B2Cl2([M]+):
506.1911, Observed: 506.1910.
138
Synthesis of 2-3Tip
Tip
Cl B
B Cl
Tip
Toluene (50 mL) was transferred into an evacuated flask containing 2-2 (1.000 g, 2.94 mmol)
and CuTip (1.572 g, 5.89 mmol) at –78 °C. The resulting mixture was stirred at 65 °C for 16 h.
After this period of time, the solution turned orange with a white solid in suspension. The
mixture was filtered at that temperature and the solvent was removed in vacuo. Hexanes were
transferred and the suspension was filtered at room temperature to yield 2-3Tip (1.430 g) as an
off-white solid in 72%. 1H NMR (CD2Cl2): δ 8.01 (d, J = 7.4 Hz, 2H), 7.45 (td, J = 7.5, 1.5 Hz,
2H), 7.36 (td, J = 7.6, 1.4 Hz, 2H), 7.04 (s, 4H), 7.00 (broad d, J = 7.8 Hz, 2H), 2.94 (hept, J =
6.9 Hz, 2H), 2.60 (hept, J = 6.7 Hz, 4H), 1.30 (d, J = 6.9 Hz, 12H), 1.18 (broad d, J = 6.7 Hz,
13
24H). C{1H} NMR (CD2Cl2): δ 150.37, 149.45, 138.73, 135.10, 133.53, 130.54, 127.93,
11
121.18, 96.78, 36.28, 34.77, 24.47, 24.22. B NMR (CD2Cl2): δ 66.3. HRMS: Calcd for
C44H54B2Cl2 ([M]+): 674.3789, Observed: 674.3784.
Synthesis of potassium naphthalenide (KNaph)
The naphthalenide solutions were prepared according to the following procedure: in the
glovebox, a mixture of potassium (1 eq.) and naphthalene (1.1 eq.) in THF was stirred in a 20
mL scintillation vial for 4 hr. The green solution was added via syringe to the reaction flask. For
each reduction the correct amount of KNaph was prepared.
139
Synthesis of Potassium Graphite (KC8)
In a two-necked round-bottomed flask flushed with argon and equipped with a magnetic stirrer,
graphite (5.00 g) was flame dried and heated to 170 ºC. After 15 min, potassium (2.03 g) was
added in small pieces and the stirring at 170 ºC was continued until a bronze-coloured potassium
graphite was formed (30 min). The reagent was cooled to room temperature and stored under
argon in the glovebox.124
Synthesis of 2-4Tip
Tip
B
B
Tip
A mixture of potassium metal (39.0 mg, 1.00 mmol) and naphthalene (133 mg, 1.00 mmol) in
THF (14 mL) was stirred at room temperature under argon for 4 h. The produced solution of
potasium naphthalenide was added to a solution of 2-3Tip (350 mg, 0.518 mmol) in THF (40 mL)
at –78 °C and the solution was stirred for 2 h at room temperature (trying to avoid light as much
as possible). After this period of time, the solution turned brown-yellowish. Solvent and
naphthalene were removed in vacuo. The dark yellow solid was suspended in hexanes and
filtered at room temperature to afford 2-4Tip (0.175 g) as a yellow solid in 55% yield. The solid
was stored in an amber vial at –35 °C 1H NMR (CD2Cl2): δ 7.51 (dt, J = 7.0, 1.2 Hz, 2H), 7.18
(td, J = 7.5, 1.2 Hz, 2H), 7.15 – 7.06 (m, 6H), 6.43 (dt, J = 7.5, 1.1 Hz, 2H), 2.98 (hept, J = 6.9
13
Hz, 2H), 2.92 (hept, J = 6.8 Hz, 4H), 1.34 (d, J = 6.9 Hz, 12H), 1.18 (s, 24H). C{1H} NMR
(CD2Cl2): δ 169.29, 156.46, 150.52, 150.41, 147.09, 135.44, 129.71, 128.29, 121.54, 120.53,
35.74, 35.02, 25.06, 24.36 (Only two peaks for carbon atoms bonded to the boron atom were
140
observed due to quadrupolar relaxation). 11B NMR (CD2Cl2): δ 70.1. HRMS: Calcd for C44H54B2
([M]+): 604.4433, Observed: 604.4412.
Synthesis of 2-5Tip
Tip
B
B
Tip
Compound 2-4Tip (70 mg) was dissolved in dichloromethane (4 mL). The yellow solution was
placed in a quartz cuvette for UV-vis spectroscopy with a Teflon tap. The solution was irradiated
under UV light (254 nm) for 12 h at room temperature. After this period of time, the solution
turned dark green. Solvent was evaporated in vacuo. In the glove box the green solid was
suspended in cold hexanes. The suspension was left at –35 °C for 30 min. and filtered to give 2-
5Tip (35 mg) as a dark green solid in 50% yield. 1H NMR (CD2Cl2): δ 7.23 – 7.15 (m, 2H), 7.07
(s, 2H), 7.04 (ddd, JH-H = 8.2, 7.1, 1.3 Hz, 2H), 6.93 (ddd, J = 7.8, 6.7, 1.0 Hz, 2H), 6.53 (dd, J =
7.1, 0.9 Hz, 2H), 2.96 (hept, J = 6.9 Hz, 2H), 2.69 (hept, J = 6.7 Hz, 4H), 1.33 (d, J = 6.9 Hz,
12H), 1.20 (dd, J = 6.7, 4.9 Hz, 24H). 13C201 NMR (CD2Cl2): δ 176.17, 151.89, 150.20, 149.80,
144.21, 135.66, 134.54, 134.27, 128.25, 121.76, 120.59, 53.84, 36.50, 34.81, 25.01, 24.73, 24.27.
11
B NMR (CD2Cl2): δ 68.6 HRMS: Calcd for C44H54B2 ([M]+): 604.4412, Observed: 604.4407.
6.2.2 Photoisomerization Details
General procedures for NMR monitoring of the photoisomerization of 2-4Tip: The
photoisomerization was carried out by preparing a CD2Cl2 (dried over CaH) solution (~0.016 M)
in a quartz NMR tube under argon. The solution was placed under UV light (254 nm) at room
141
temperature and the exposure time was recorded. After each exposure period, the NMR spectrum
was recorded.
0 min
30 min
120 min
240 min
360 min
600 min
3.3 3.1 2.9 2.7 2.5 2.3 2.1 1.9 1.7 1.5 1.3 1.1 0.9 0.7 0.5 0.3
0 min
30 min
120 min
240 min
360 min
600 min
7.9 7.8 7.7 7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7 6.6 6.5 6.4
Figure 6-1 Photochemical reaction of 2-4Tip monitored by 1H NMR spectroscopy. Alkyl region
(top) and aromatic region (bottom)
142
Synthesis of 3-5Tip
THF
Tip
K
B
B
Tip K
THF
A mixture of potassium metal (12.9 mg, 0.33 mmol) and naphthalene (133 mg, 0.36 mmol) in
potassium naphthalenide was added to a solution of 2-4Tip (100 mg, 0.165 mmol) in THF (30
mL) at –78 °C and the solution was stirred for 2 h at room temperature. After this period of time,
the solution turned brown. Solvent and naphthalene were removed in vacuo. The brown solid
was dissolved in THF (6 mL), layered with hexanes (6 mL) and allowed to crystallize for 6 days
at –35 ºC. Compound 3-5Tip (0.081 g) was isolated as a dark brown solid in 61% yield. 1H NMR
(400 MHz, THF-d8) δ 6.77 (s, 4H), 5.47 (s, 2H), 5.29 (s, 5.7 Hz, 2H), 5.09 (s, 2H), 4.21 (s, 2H),
3.59 (4H buried under the proteo THF signal), 2.76 (s, 2H), 1.19 (s, 36H) all the signals in the 1H
13
NMR spectrum are broad. C{1H} NMR (101 MHz, THF-d8) δ 176.66, 167.45 (small and
broad), 152.17, 145.42, 143.42 (small and broad), 129.36 (small and broad), 125.94, 120.72,
11
119.29, 113.32, 101.04, 35.59, 34.06, 26.55, 24.96. B NMR (128 MHz, THF-d8): δ 38.7.
HRMS: Calcd for C44H54B2 [[M]+-(K+THF)]: 604.4431, Observed: 604.4423. Anal. Calcd. for
C52H70B2K2O2: C, 75.53; H, 8.53. Found: C, 75.89; H, 8.51.
143
Synthesis of 3-6Tip from 3-5Tip (acid promoted isomerization)
THF
Tip
K
B
B
Tip K
THF
In a 25 mL round-bottomed flask compound 3-5Tip (70 mg, 0.085 mmol) was dissolved in THF
(15 mL). A solution of t-butanol (1.1 mL, 0.093 mmol, 87.7 mM) in THF was slowly added to
the solution of 3-5Tip while stirring at 0 ºC. The cold bath was removed and the solution was
stirred for 1 h at room temperature. The solution slowly changed from dark brown to dark red
and the solvent was removed under vacuum. The dark red solid was dissolved in 1 mL of THF
and layered with 1 mL of hexanes and stored at –35 ºC for 3 days. Removal of the mother liquor
yielded compound 3-6Tip as red crystals (62 mg, 89%). 1H NMR (600 MHz, THF-d8) δ 6.94 (s,
4H), 6.80 – 6.62 (m, 4H), 6.32 – 6.22 (m, 2H), 6.09 (td, J = 7.0, 1.2 Hz, 2H), 3.41 (hept, J = 7.0
Hz, 4H), 2.87 (hept, J = 6.9 Hz, 2H), 1.30 (d, J = 6.9 Hz, 12H), 1.14 (d, J = 7.0 Hz, 12H), 1.12
13
(d, J = 6.9 Hz, 12H). C{1H} NMR (151 MHz, THF) δ 155.13 (small and broad), 154.20,
151.27, 146.77 (small and broad), 145.06, 137.90 (small and broad), 129.86, 123.51, 120.63,
119.42, 118.26, 35.53, 34.57, 26.55, 25.03. 11B NMR (128 MHz, THF-d8): δ 32.0. HRMS: Calcd
for C44H54B2 [[M]+-(K+THF)]: 604.4431, Observed: 604.4413. Anal. Calcd. for C52H70B2K2O2:
C, 75.53; H, 8.53. Found: C, 75.60; H, 8.63.
144
Synthesis of 3-6Tip
THF
Tip
K
B
B
Tip K
THF
A mixture of potassium metal (3.0 mg, 0.051 mmol) and naphthalene (6.4 mg, 0.050 mmol) in
potassium naphthalenide was added to a solution of 2-5Tip (15 mg, 0.0248 mmol) in THF (5 mL)
at -78 °C and the solution was stirred for 2 h at room temperature. After this period of time, the
solution turned red. Solvent and naphthalene were removed in vacuo. The red solid was
dissolved in THF (1 mL), layered with hexanes (1 mL) and allowed to crystallize for 6 days at –
35 ºC. Compound 3-6Tip (12.0 mg) was isolated as a red solid in 55% yield. Spectroscopic data
are identical to 3-6Tip prepared by isomerization of 3-5Tip.
Synthesis of 3-7Tip
H Tip
H
B
B
Tip
(5 mL). 4-methoxyphenol (17 mg, 0.137 mmol) was dissolved in THF (1 mL) and added
dropwise to the solution of 3-5Tip while stirring. After the addition was complete the solution
turned colorless. Solvent was removed under vacuum. The crude white solid was dissolved in
boiling hexanes (6 mL) and filtered through a fine frit to remove the potassium 4-
methoxyphenoxide produced. After removal of the solvent, the crude white solid was dissolved
145
in boiling hexanes (3 mL) and stored at –35 ºC for 3 days. Removal of the mother liquor yielded
compound 3-7Tip as a white solid (29 mg, 72%). 1H NMR (600 MHz, CD2Cl2) δ 7.52 (ddd, J =
7.4, 1.3, 0.8 Hz, 2H), 7.38 (ddd, J = 7.8, 7.2, 1.4 Hz, 2H), 7.16 – 7.10 (m, 4H), 7.10 (d, J = 1.5
Hz, 2H), 6.86 (d, J = 1.6 Hz, 1H), 4.16 (s, 2H), 2.93 (hept, J = 7.1 Hz, 2H), 2.70 – 2.60 (m, J =
6.8 Hz, 2H), 1.41 (d, J = 6.7 Hz, 6H), 1.31 (d, J = 2.8 Hz, 6H), 1.30 (d, J = 2.8 Hz, 6H), 1.28
(hept, J = 6.9 Hz, 2H), 1.21 (d, J = 6.8 Hz, 6H), 0.77 (d, J = 6.7 Hz, 6H), 0.33 (d, J = 6.7 Hz,
13
6H). C{1H} NMR (151 MHz, CD2Cl2) δ 163.54, 149.64, 148.97, 148.91, 145.05 (small and
broad), 136.47 (small and broad), 135.15, 134.89, 125.62, 125.46, 120.17, 120.09, 57.86, 53.84,
11
36.52, 35.93, 34.72, 25.60, 24.86, 24.68, 24.32, 24.25, 22.37. B NMR (193 MHz, CD2Cl2) δ
77.0. HRMS: Calcd for C44H56B2 ([M]+): 606.4568, Observed: 606.4573.
Synthesis of 2-5Tip from 3-6Tip
Tip
B
B
Tip
In a 25 mL round-bottomed flask compound 3-6Tip (80 mg, 0.0967 mmol) and AgSO3CF3 (49.7
mg, 0.193 mmol) were dissolved in THF (15 mL) at -78 ºC. The solution was stirred for 10
minutes at room temperature. After this period of time the solution turned brown-greenish.
Solvent was removed in vacuo. In the glove box the greenish solid was dissolved in
dichloromethane (4 mL) and filtered through a sintered glass filter to remove the potassium
triflate produced in the reaction. Solvent was removed in vacuo and the solid was re-dissolved in
dichloromethane (2 mL), layered with hexanes (2 mL) and left in the fridge at –35 ºC for 2 days.
146
Compound 2-5Tip (0.035 g) was isolated as green crystals in 60% yield. The spectroscopic data
are consistent with previously published data.2
Synthesis of 3-2Tip
(THF)n
K Tip
B
B
Tip
In a 20 mL scintillation vial compound 2-4Tip (27 mg, 0.0447 mmol) was dissolved in THF (8
mL). KC8 (6.2 mg, 0.0459 mmol) was added to the solution of 2-4Tip. After the addition was
complete the solution turned violet. The solution was filtered through a sintered glass filter to
remove the graphite and the solvent was removed under vacuum. The crude brown-violet solid
was dissolved THF (1 mL) and the solution was layered with hexanes (1.5 mL). The solution
was stored at -35 ºC for 21 days. Removal of the mother liquor yielded compound 3-2Tip (25 mg)
as very sensitive violet crystals. Due to the high sensitivity of the crystals elemental analysis
could not be determined.
Synthesis of 3-3Tip
(THF)n
K Tip
B
B
Tip
In a 20 mL scintillation vial compound 2-5Tip (10 mg, 0.0165 mmol) was dissolved in THF (3
mL). KC8 (2.2 mg, 0.0163 mmol) was added to the solution of 2-5Tip. After the addition was
147
complete the solution turned blue. The solution was filtered through a sintered glass filter to
remove the graphite and the solvent was removed under vacuum. The crude blue solid was
dissolved THF (0.5 mL) and the solution was layered with hexanes (1 mL). The solution was
stored at –35 ºC for 5 days. After removal of the mother liquor the blue crystals were dried under
vacuum, yielding 9.5 mg of compound 3-3Tip. Due to the high sensitivity of the crystals
elemental analysis could not be determined.
Synthesis of 3-4Tip
CoCp*2 Tip
B
B
Tip
In a 3 mL vial compound 2-5Tip (4.0 mg, 0.006 mmol) was dissolved in dichloromethane (1 mL)
and added into another vial containing decamethylcobaltocene. After the addition was complete
the solution turned blue. The solution was layered with hexanes (1 mL) and allowed to
crystallize for 6 days at –35 ºC. After removal of the mother liquor the blue crystals were dried
under vacuum, yielding 2.1 mg of compound 3-4Tip (34% yield). Due to the high sensitivity of
the crystals elemental analysis could not be determined.
6.3.2 EPR Spectroscopy
The structure of compounds 3-2Tip and 3-3Tip were modeled by DFT using the UB3PW91
functional with the 6-31+G(d) basis set (compounds were modeled as anionic species without the
counter cation). The hyperfine coupling constants (hfcc) were calculated using the basis set EPR-
148
II, which is optimized for their computation. The hyperfine coupling constants were used as the
initial values for the simulations and they were modified by hand until the correlation between
the simulated and the experimental spectrum was higher than 97%. Subsequently, the program
algorithm was utilized, which allowed reaching a correlation of 99.6% for 3-2Tip and 99.9% for
3-3Tip.
Figure 6-2 Experimental (black) and simulated (red) EPR spectrum of 3-2Tip (top). Experimental
(black) and simulated (red) EPR spectrum of 3-3Tip (bottom)
149
6.3.2.1 Titration Experiment
Compound 3-5Tip was dissolved in THF in an EPR tube and the spectrum was measured (Figure
6-3, series “1”). Approximately 1 mg of compound 2-4Tip was dissolved in 1 mL of THF and a
couple of drops were added into the EPR tube and the spectrum was measured again (Figure
6-3), series “2”). This procedure was repeated two more times (Figure 6-3, series “3” and “4”
respectively). Along with the augmentation of the EPR signal there is also a change in color of
the solution from dark brown to violet. Since compound 3-5Tip is capable of reducing compound
2-4Tip, this experiments generates the radical 3-2Tip in situ upon subsequent additions of 2-4Tip to
the EPR tube containing 3-5Tip.
1$
2$
3$
4$
3325$ 3330$ 3335$ 3340$ 3345$ 3350$ 3355$ 3360$ 3365$ 3370$
Magne&c(Field((G)(
indicate a qualitative increment in the amount of compound 2-4Tip added to the EPR tube
containing 3-5Tip.
150
Synthesis of 4-1Tip (from 3-5Tip)
KO
O
Tip B B Tip
O
OK
(15 mL). The resulting brown solution was degassed by freeze−pump−thaw cycles. CO2 was
expanded into the flask (1 atm) and the flask was warmed to room temperature and allowed to
stand for 30 minutes. The flask was evacuated to remove the solvent, giving a yellow-orange
solid. In the glove box, the solid was suspended in cold pentane, filtered and washed with cold
pentane twice. Compound 4-1Tip was isolated as a yellow solid (28 mg, 71%). 1H NMR (CD2Cl2)
δ 7.32 (dd, J = 7.5, 1.5 Hz, 2H), 7.21 (ddd, J = 8.4, 6.8, 1.5 Hz, 2H), 6.98 (s, 4H), 6.81 (d, J = 8.4
Hz, 2H), 6.60 (td, J = 7.1, 1.1 Hz, 2H), 2.88 (hept, J = 6.9 Hz, 2H), 2.73 (hept, J = 6.8 Hz, 2H),
2.66 (hept, J = 6.7 Hz, 2H), 1.36 (d, J = 6.6 Hz, 6H), 1.24 (dd, J = 7.0, 2.1 Hz, 18H), 0.99 (d, J =
6.8 Hz, 6H), 0.79 (d, J = 7.0 Hz, 6H). 13C{1H} NMR (CD2Cl2) δ 165.11, 151.97, 151.03, 149.69,
149.23, 139.05, 134.45, 133.92, 123.01, 120.33, 120.22, 120.07, 118.19, 85.20, 53.84, 35.36,
34.81, 34.78, 25.99, 25.66, 25.13, 24.44, 24.07. HRMS: Calcd for C46H55B2O4K2[[M]++H]:
771.3561, Observed: 771.3565.
Synthesis of 4-1Tip (from 3-6Tip)
(15 mL). The resulting red solution was degassed by freeze−pump−thaw cycles. CO2 was
expanded into the flask (1 atm) and the flask was warmed to room temperature and allowed to
151
stand for 30 minutes. The flask was evacuated to remove the solvent, giving a yellow solid. In
the glove box, the solid was suspended in cold pentane, filtered and washed with cold pentane
twice. Compound 4-1Tip was isolated as a yellow solid (30 mg, 76%). Spectroscopic data are
identical to 4-1Tip prepared from 3-5Tip.
Synthesis of 4-2Tip
KO
Tip
B
K
B
Tip
In a 25 mL thick-walled glass vessel compound 3-6Tip (30 mg, 0.036 mmol) was dissolved in
THF (10 mL). The resulting red solution was degassed by freeze−pump−thaw cycles. CO was
expanded into the flask (1 atm), the vessel was closed and allowed to reach room temperature.
The solution was stirred at 70 ºC for 24 h. At room temperature, the vessel was evacuated to
remove the solvent. In the glove box, the dark blue solid was dissolved in THF (1 mL), layered
with hexanes (1.5 mL) and allowed to crystallize for 6 days at –35 ºC. Compound 4-2Tip (0.020
g) was isolated as dark blue crystals in 62% yield. 1H NMR (THF-d8) δ 8.17 (d, J = 7.3 Hz, 1H),
7.39 (d, J = 8.5 Hz, 1H), 7.05 (s, 2H), 6.96 (s, 2H), 6.92 (d, J = 7.8 Hz, 1H), 6.76 (t, J = 6.8 Hz,
1H), 6.69 (d, J = 6.8 Hz, 1H), 6.47 (t, J = 7.2 Hz, 1H), 6.33 (t, J = 7.3 Hz, 1H), 6.09 (t, J = 6.8
Hz, 1H), 3.10 (hept, J = 6.8 Hz, 2H), 3.03 (hept, J = 6.8 Hz, 2H), 2.96 – 2.85 (m, 2H), 1.31 (d, J
13
= 7.0 Hz, 6H), 1.26 (d, J = 6.5 Hz, 12H), 1.09 – 1.02 (m, 18H). C{1H} NMR (THF-d8) δ
155.84, 153.03, 151.24, 150.17, 146.98, 146.35, 145.53, 142.48, 137.91, 135.83, 130.24, 127.89,
127.73, 124.51, 122.92, 120.61, 119.64, 119.47, 115.97, 35.17, 35.13, 34.87, 34.47, 26.20, 25.60,
11
25.47, 25.33, 24.62, 24.58. B NMR (THF-d8) δ 46.6. HRMS: Calcd for
C46H55B2O4K2[[M]++H]: 771.3561, Observed: 771.3565.
152
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162
APPENDIX A: CRYSTALLOGRAPHIC DATA
Table A-1 Crystal data and structure refinement for 2-3Tip

Crystallographer Mike Sgro-University of Calgary
Empirical formula C44 H54 B2 Cl2
Formula weight 675.39
Temperature 293(2) K
Wavelength 0.71073 Å
Crystal system Monoclinic
Space group P 21/n
Unit cell dimensions a = 12.2290(4) Å α = 90.000(2) º
b = 8.9750(5) Å β = 101.033(2) º
c = 18.0650(6) Å γ = 90.0000(18) º
Volume 1946.08(14) Å3
Z 2
Calculated density 1.153 Mg/m3
Absorption coefficient 0.196 mm-1
F(000) 724
θ range for data collection 2.834 to 27.666 º
Limiting indices -15 <= h <= 15 ; -11 <= k <= 11 ; -23 <= l <= 23
Reflections collected / unique 14728 / 14728 [R(int) = 0.0478]
Completeness to θ = 68.04 99.2 %
Absorption correction None
Max. and min. transmission 0.8789 and 0.8299
Refinement method Full-matrix least-squares on F2
Data / restraints / parameters 4507 / 0 / 223
Goodness-of-fit on F^2 1.065
Final R indices [I>2σ(I)] R1 = 0.0645, wR2 = 0.1504
R indices (all data) R1 = 0.0798, wR2 = 0.1605
Largest diff. peak and hole 0.811 and -0.433 e Å-3
Table A-2 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Å2x 103) for 2-3Tip
Atom x y z U(eq)
B1 7152.8(1.9) 5004(3) -1025.7(1.3) 26.7(5)
C1 5111.9(1.7) 4734(3) -280.6(1.2) 29.1(4)
C10 8018.7(1.8) 8007(2) 474.5(1.2) 30.3(5)
C11 8584.5(1.8) 7206(3) 1082.7(1.2) 30.8(5)
C12 8611.5(1.8) 5671(3) 1018.2(1.2) 30.8(5)
C13 8110.4(1.7) 4943(2) 362.3(1.1) 27.4(4)
C14 6852(2) 8253(3) -822.3(1.3) 34.8(5)
C15 5876(2) 9054(3) -577.1(1.6) 50.6(7)
C16 7595(3) 9348(3) -1133.8(1.6) 51.5(7)
C17 9146(2) 8031(3) 1784.5(1.3) 43.6(6)
C18 10270(3) 8574(4) 1693.8(1.8) 69.7(1.0)
C19 9172(3) 7194(5) 2501.6(1.6) 75.2(1.1)
C2 5183.2(1.7) 3956(2) -958.4(1.1) 27.1(4)
C20 8168.0(1.9) 3262(2) 316.4(1.2) 32.1(5)
C21 7594(2) 2542(3) 902.6(1.6) 46.4(6)
C22 9358(2) 2714(3) 382.8(1.5) 44.8(6)
C3 6119.3(1.6) 4023(2) -1314.0(1.1) 24.8(4)
163
C4 6069.5(1.8) 3157(3) -1963.6(1.1) 30.2(5)
C5 5172(2) 2280(3) -2251.3(1.2) 37.0(5)
C6 4263(2) 2254(3) -1903.6(1.3) 40.1(6)
C7 4266.1(1.8) 3088(3) -1265.9(1.3) 35.9(5)
C8 7557.4(1.6) 5776(2) -252.1(1.1) 24.7(4)
C9 7501.7(1.7) 7328(2) -186.4(1.1) 27.2(4)
Cl1 8063.8(5) 5281.7(9) -1670.9(3) 50.1(2)
Table A-3 Bond lengths [Å] for 2-3Tip

C1 - C1 1.199(4) C2 - C3 1.417(3)
C1 - C2 1.427(3) C2 - C7 1.391(3)
C10 - C11 1.383(3) C20 - C21 1.522(3)
C10 - H10 0.93 C20 - C22 1.519(3)
C11 - C12 1.384(3) C20 - H20 0.98
C11 - C17 1.514(3) C21 - H21A 0.96
C12 - C13 1.389(3) C21 - H21B 0.96
C12 - H12 0.93 C21 - H21C 0.96
C13 - C20 1.514(3) C22 - H22A 0.96
C14 - C15 1.530(3) C22 - H22B 0.96
C14 - C16 1.518(3) C22 - H22C 0.96
C14 - H14 0.98 C3 - B1 1.546(3)
C15 - H15A 0.96 C3 - C4 1.399(3)
C15 - H15B 0.96 C4 - C5 1.370(3)
C15 - H15C 0.96 C4 - H4 0.93
C16 - H16A 0.96 C5 - C6 1.377(3)
C16 - H16B 0.96 C5 - H5 0.93
C16 - H16C 0.96 C6 - C7 1.374(3)
C17 - C18 1.497(4) C6 - H6 0.93
C17 - C19 1.493(4) C7 - H7 0.93
C17 - H17 0.98 C8 - B1 1.553(3)
C18 - H18A 0.96 C8 - C13 1.400(3)
C18 - H18B 0.96 C8 - C9 1.400(3)
C18 - H18C 0.96 C9 - C10 1.381(3)
C19 - H19A 0.96 C9 - C14 1.514(3)
C19 - H19B 0.96 Cl1 - B1 1.777(2)
C19 - H19C 0.96
Table A-4 Bond angles [º] for 2-3Tip

C1 - C1 - C2 169.2(3) C22 - C20 - C21 111.7(2)
C10 - C11 - C12 117.85(19) C22 - C20 - H20 107.5
C10 - C11 - C17 119.3(2) C3 - B1 - C8 130.99(18)
C10 - C9 - C14 120.1(2) C3 - B1 - Cl1 115.68(16)
C10 - C9 - C8 119.37(19) C3 - C2 - C1 123.73(19)
C11 - C10 - H10 118.9 C3 - C4 - H4 118.6
C11 - C12 - C13 121.8(2) C4 - C3 - B1 120.01(18)
C11 - C12 - H12 119.1 C4 - C3 - C2 116.55(18)
C11 - C17 - H17 106.2 C4 - C5 - C6 119.7(2)
C12 - C11 - C17 122.9(2) C4 - C5 - H5 120.2
C12 - C13 - C20 119.88(19) C5 - C4 - C3 122.7(2)
C12 - C13 - C8 119.5(2) C5 - C4 - H4 118.6
164
C13 - C12 - H12 119.1 C5 - C6 - H6 120
C13 - C20 - C21 110.64(19) C6 - C5 - H5 120.2
C13 - C20 - C22 111.9(2) C6 - C7 - C2 120.8(2)
C13 - C20 - H20 107.5 C6 - C7 - H7 119.6
C13 - C8 - B1 119.82(19) C7 - C2 - C1 116.09(18)
C13 - C8 - C9 119.19(18) C7 - C2 - C3 120.18(19)
C14 - C15 - H15A 109.5 C7 - C6 - C5 120.0(2)
C14 - C15 - H15B 109.5 C7 - C6 - H6 120
C14 - C15 - H15C 109.5 C8 - B1 - Cl1 113.32(16)
C14 - C16 - H16A 109.5 C8 - C13 - C20 120.61(18)
C14 - C16 - H16B 109.5 C8 - C9 - C14 120.55(19)
C14 - C16 - H16C 109.5 C9 - C10 - C11 122.3(2)
C15 - C14 - H14 107.5 C9 - C10 - H10 118.9
C16 - C14 - C15 111.0(2) C9 - C14 - C15 111.31(19)
C16 - C14 - H14 107.5 C9 - C14 - C16 111.8(2)
C17 - C18 - H18A 109.5 C9 - C14 - H14 107.5
C17 - C18 - H18B 109.5 C9 - C8 - B1 120.49(18)
C17 - C18 - H18C 109.5 H15A - C15 - H15B 109.5
C17 - C19 - H19A 109.5 H15A - C15 - H15C 109.5
C17 - C19 - H19B 109.5 H15B - C15 - H15C 109.5
C17 - C19 - H19C 109.5 H16A - C16 - H16B 109.5
C18 - C17 - C11 110.2(2) H16A - C16 - H16C 109.5
C18 - C17 - H17 106.2 H16B - C16 - H16C 109.5
C19 - C17 - C11 114.3(2) H18A - C18 - H18B 109.5
C19 - C17 - C18 113.0(3) H18A - C18 - H18C 109.5
C19 - C17 - H17 106.2 H18B - C18 - H18C 109.5
C2 - C3 - B1 123.43(18) H19A - C19 - H19B 109.5
C2 - C7 - H7 119.6 H19A - C19 - H19C 109.5
C20 - C21 - H21A 109.5 H19B - C19 - H19C 109.5
C20 - C21 - H21B 109.5 H21A - C21 - H21B 109.5
C20 - C21 - H21C 109.5 H21A - C21 - H21C 109.5
C20 - C22 - H22A 109.5 H21B - C21 - H21C 109.5
C20 - C22 - H22B 109.5 H22A - C22 - H22B 109.5
C20 - C22 - H22C 109.5 H22A - C22 - H22C 109.5
C21 - C20 - H20 107.5 H22B - C22 - H22C 109.5

Crystallographer Masood Parvez-University of Calgary
Empirical formula C44 H54 B2
Space group C 2/c
Unit cell dimensions a = 17.084(5) Å α = 90 º
b = 11.051(5) Å β = 96.17(3) º
c = 19.762(7) Å γ = 90 º
Volume 3709(2) Å3
Z 4
165
F(000) 1312
Limiting indices -21<=h<=21, -13<=k<=13, -24<=l<=24
Completeness to θ = 26.43 99.8 %
Atom x y z U(eq)
B(1) 421(2) 5526(4) 1521(2) 41(1)
C(1) -400(2) 5603(4) 1076(2) 50(1)
C(2) -841(3) 5587(5) 446(2) 68(1)
C(3) -1645(3) 5545(5) 425(2) 71(2)
C(4) -2012(2) 5504(4) 1018(2) 62(1)
C(5) -1596(2) 5534(4) 1657(2) 50(1)
C(6) -783(2) 5584(4) 1676(2) 44(1)
C(7) -57(2) 5601(4) 2162(2) 43(1)
C(8) 1299(2) 5243(3) 1420(2) 32(1)
C(13) 1583(2) 4080(3) 1555(2) 38(1)
C(9) 1800(3) 6136(4) 1224(2) 55(1)
C(14) 1765(5) 7413(6) 1059(4) 48(2)
C(15) 1472(4) 8167(6) 1617(3) 109(2)
C(16) 1304(3) 7667(7) 362(3) 104(2)
C(9') 1800(3) 6136(4) 1224(2) 55(1)
C(14') 1316(4) 7392(7) 1079(4) 48(2)
C(15') 1472(4) 8167(6) 1617(3) 109(2)
C(16') 1304(3) 7667(7) 362(3) 104(2)
C(10) 2681(6) 5573(10) 1201(5) 31(2)
C(11) 2874(5) 4368(8) 1333(4) 26(2)
C(12) 2291(7) 3611(10) 1529(7) 31(2)
C(17) 3702(4) 3884(7) 1255(4) 37(1)
C(18) 4290(40) 4540(40) 1670(30) 65(8)
C(19) 3840(30) 3840(40) 500(30) 67(6)
C(10') 2490(5) 6120(8) 1140(5) 31(2)
C(11') 2870(5) 5009(10) 1263(4) 26(2)
C(12') 2437(7) 4023(11) 1442(7) 31(2)
166
C(17') 3738(4) 4883(7) 1170(4) 37(1)
C(18') 4240(40) 4270(50) 1810(30) 65(8)
C(19') 3860(30) 4150(40) 560(30) 67(6)
C(21) 792(3) 2230(5) 1193(3) 81(2)
C(20) 1028(3) 3103(4) 1760(2) 62(1)
C(22) 1547(6) 2346(10) 2309(6) 64(3)
C(20') 1028(3) 3103(4) 1760(2) 62(1)
C(22') 1143(5) 2567(9) 2483(5) 55(2)

B(1)-C(8) 1.565(5) C(12)-H(12) 0.95
B(1)-C(1) 1.575(5) C(17)-C(18) 1.42(6)
B(1)-C(7) 1.581(5) C(17)-C(19) 1.55(5)
C(1)-C(2) 1.385(5) C(17)-H(17) 1
C(1)-C(6) 1.416(5) C(18)-H(18A) 0.98
C(2)-C(3) 1.371(6) C(18)-H(18B) 0.98
C(2)-H(2) 0.95 C(18)-H(18C) 0.98
C(3)-C(4) 1.388(6) C(19)-H(19A) 0.98
C(3)-H(3) 0.95 C(19)-H(19B) 0.98
C(4)-C(5) 1.381(5) C(19)-H(19C) 0.98
C(4)-H(4) 0.95 C(10')-C(11') 1.397(11)
C(5)-C(6) 1.387(5) C(10')-H(10') 0.95
C(5)-H(5) 0.95 C(11')-C(12') 1.385(11)
C(6)-C(7) 1.485(5) C(11')-C(17') 1.519(10)
C(7)-C(7)#1 1.330(7) C(12')-H(12') 0.95
C(8)-C(9) 1.389(5) C(17')-C(19') 1.49(4)
C(8)-C(13) 1.390(5) C(17')-C(18') 1.60(5)
C(13)-C(12) 1.322(14) C(17')-H(17') 1
C(13)-C(12') 1.500(13) C(18')-H(18D) 0.98
C(13)-C(20) 1.520(6) C(18')-H(18E) 0.98
C(9)-C(14) 1.448(7) C(18')-H(18F) 0.98
C(9)-C(10) 1.633(11) C(19')-H(19D) 0.98
C(14)-C(15) 1.510(10) C(19')-H(19E) 0.98
C(14)-C(16) 1.537(10) C(19')-H(19F) 0.98
C(14)-H(14) 1 C(21)-C(20) 1.500(6)
C(15)-H(15A) 0.98 C(21)-H(21A) 0.98
C(15)-H(15B) 0.98 C(21)-H(21B) 0.98
C(15)-H(15C) 0.98 C(21)-H(21C) 0.98
C(16)-H(16A) 0.98 C(20)-C(22) 1.568(11)
C(16)-H(16B) 0.98 C(20)-H(20) 1
C(16)-H(16C) 0.98 C(22)-H(22A) 0.98
C(14')-H(14') 1 C(22)-H(22B) 0.98
C(10)-C(11) 1.390(11) C(22)-H(22C) 0.98
C(10)-H(10) 0.95 C(22')-H(22D) 0.98
C(11)-C(12) 1.387(9) C(22')-H(22E) 0.98
C(11)-C(17) 1.535(11) C(22')-H(22F) 0.98
167
C(8)-B(1)-C(1) 138.3(3) C(18)-C(17)-C(19) 114(3)
C(8)-B(1)-C(7) 134.2(3) C(11)-C(17)-C(19) 110.6(17)
C(1)-B(1)-C(7) 86.6(3) C(18)-C(17)-H(17) 106.9
C(2)-C(1)-C(6) 119.8(4) C(11)-C(17)-H(17) 106.9
C(2)-C(1)-B(1) 150.2(4) C(19)-C(17)-H(17) 106.9
C(6)-C(1)-B(1) 89.7(3) C(17)-C(18)-H(18A) 109.5
C(3)-C(2)-C(1) 118.3(4) C(17)-C(18)-H(18B) 109.5
C(3)-C(2)-H(2) 120.8 H(18A)-C(18)-H(18B) 109.5
C(1)-C(2)-H(2) 120.8 C(17)-C(18)-H(18C) 109.5
C(2)-C(3)-C(4) 121.2(4) H(18A)-C(18)-H(18C) 109.5
C(2)-C(3)-H(3) 119.4 H(18B)-C(18)-H(18C) 109.5
C(4)-C(3)-H(3) 119.4 C(17)-C(19)-H(19A) 109.5
C(5)-C(4)-C(3) 122.5(4) C(17)-C(19)-H(19B) 109.5
C(5)-C(4)-H(4) 118.8 H(19A)-C(19)-H(19B) 109.5
C(3)-C(4)-H(4) 118.8 C(17)-C(19)-H(19C) 109.5
C(4)-C(5)-C(6) 116.2(4) H(19A)-C(19)-H(19C) 109.5
C(4)-C(5)-H(5) 121.9 H(19B)-C(19)-H(19C) 109.5
C(6)-C(5)-H(5) 121.9 C(11')-C(10')-H(10') 122.2
C(5)-C(6)-C(1) 122.0(3) C(12')-C(11')-C(10') 118.9(9)
C(5)-C(6)-C(7) 141.6(3) C(12')-C(11')-C(17') 120.9(9)
C(1)-C(6)-C(7) 96.4(3) C(10')-C(11')-C(17') 120.1(9)
C(7)#1-C(7)-C(6) 132.1(4) C(11')-C(12')-C(13) 124.1(10)
C(7)#1-C(7)-B(1) 140.7(4) C(11')-C(12')-H(12') 118
C(6)-C(7)-B(1) 87.1(3) C(13)-C(12')-H(12') 118
C(9)-C(8)-C(13) 119.8(3) C(19')-C(17')-C(11') 111.6(19)
C(9)-C(8)-B(1) 121.5(4) C(19')-C(17')-C(18') 108(3)
C(13)-C(8)-B(1) 118.7(3) C(11')-C(17')-C(18') 113(2)
C(12)-C(13)-C(8) 131.1(5) C(19')-C(17')-H(17') 108.2
C(12)-C(13)-C(12') 21.5(6) C(11')-C(17')-H(17') 108.2
C(8)-C(13)-C(12') 109.6(5) C(18')-C(17')-H(17') 108.2
C(12)-C(13)-C(20) 109.4(5) C(17')-C(18')-H(18D) 109.5
C(8)-C(13)-C(20) 119.5(3) C(17')-C(18')-H(18E) 109.5
C(12')-C(13)-C(20) 130.8(5) H(18D)-C(18')-H(18E) 109.5
C(8)-C(9)-C(14) 137.9(5) C(17')-C(18')-H(18F) 109.5
C(8)-C(9)-C(10) 109.6(5) H(18D)-C(18')-H(18F) 109.5
C(14)-C(9)-C(10) 112.4(6) H(18E)-C(18')-H(18F) 109.5
C(9)-C(14)-C(15) 112.5(6) C(17')-C(19')-H(19D) 109.5
C(9)-C(14)-C(16) 112.6(6) C(17')-C(19')-H(19E) 109.5
C(15)-C(14)-C(16) 112.0(6) H(19D)-C(19')-H(19E) 109.5
C(9)-C(14)-H(14) 106.4 C(17')-C(19')-H(19F) 109.5
C(15)-C(14)-H(14) 106.4 H(19D)-C(19')-H(19F) 109.5
C(16)-C(14)-H(14) 106.4 H(19E)-C(19')-H(19F) 109.5
C(14)-C(15)-H(15A) 109.5 C(20)-C(21)-H(21A) 109.5
C(14)-C(15)-H(15B) 109.5 C(20)-C(21)-H(21B) 109.5
H(15A)-C(15)-H(15B) 109.5 H(21A)-C(21)-H(21B) 109.5
C(14)-C(15)-H(15C) 109.5 C(20)-C(21)-H(21C) 109.5
H(15A)-C(15)-H(15C) 109.5 H(21A)-C(21)-H(21C) 109.5
H(15B)-C(15)-H(15C) 109.5 H(21B)-C(21)-H(21C) 109.5
C(14)-C(16)-H(16A) 109.5 C(21)-C(20)-C(13) 112.6(4)
C(14)-C(16)-H(16B) 109.5 C(21)-C(20)-C(22) 105.0(6)
H(16A)-C(16)-H(16B) 109.5 C(13)-C(20)-C(22) 104.0(5)
C(14)-C(16)-H(16C) 109.5 C(21)-C(20)-H(20) 111.6
H(16A)-C(16)-H(16C) 109.5 C(13)-C(20)-H(20) 111.6
H(16B)-C(16)-H(16C) 109.5 C(22)-C(20)-H(20) 111.6
168
C(11)-C(10)-C(9) 124.1(7) C(20)-C(22)-H(22A) 109.5
C(11)-C(10)-H(10) 118 C(20)-C(22)-H(22B) 109.5
C(9)-C(10)-H(10) 118 H(22A)-C(22)-H(22B) 109.5
C(12)-C(11)-C(10) 117.8(9) C(20)-C(22)-H(22C) 109.5
C(12)-C(11)-C(17) 121.0(9) H(22A)-C(22)-H(22C) 109.5
C(10)-C(11)-C(17) 121.2(8) H(22B)-C(22)-H(22C) 109.5
C(13)-C(12)-C(11) 117.6(9) H(22D)-C(22')-H(22E) 109.5
C(13)-C(12)-H(12) 121.2 H(22D)-C(22')-H(22F) 109.5
C(11)-C(12)-H(12) 121.2 H(22E)-C(22')-H(22F) 109.5

Empirical formula C46 H58 B2 Cl4
Crystal system Triclinic
Space group P -1
Unit cell dimensions a = 8.8623(3) Å α = 90.416(2)º
b = 10.0647(3) Å β = 102.494(2)º
c = 13.5684(5) Å γ = 112.145(2)º
Volume 1089.14(6) Å3
Z 1
F(000) 412
θ range for data collection 1.54 to 27.52º
Completeness to θ = 25.00 º 99.5 %
Atom x y z U(eq)
B(1) 6849(4) 836(3) 1148(2) 29(1)
C(1) 5459(3) 710(3) 169(2) 29(1)
C(2) 4840(3) 1652(3) -489(2) 29(1)
C(3) 3466(3) 805(3) -1287(2) 30(1)
C(4) 2689(4) 1476(3) -1976(2) 37(1)
C(5) 3259(4) 2987(3) -1893(2) 37(1)
C(6) 4593(4) 3794(3) -1122(2) 37(1)
C(7) 5410(3) 3137(3) -410(2) 33(1)
169
C(8) 8228(3) 2234(3) 1796(2) 28(1)
C(9) 7914(3) 2908(3) 2594(2) 28(1)
C(10) 9169(3) 4168(3) 3130(2) 32(1)
C(11) 10715(3) 4787(3) 2892(2) 35(1)
C(12) 11006(3) 4119(3) 2097(2) 37(1)
C(13) 9788(3) 2849(3) 1552(2) 33(1)
C(14) 6244(3) 2213(3) 2888(2) 32(1)
C(15) 6374(4) 1274(3) 3758(3) 44(1)
C(16) 5543(4) 3306(3) 3156(3) 42(1)
C(17) 12041(4) 6181(3) 3484(3) 48(1)
C(18) 12183(6) 7447(4) 2865(4) 84(2)
C(19) 13746(4) 6105(4) 3851(3) 58(1)
C(20) 10124(4) 2137(3) 680(2) 45(1)
C(21) 10472(6) 3122(5) -161(3) 78(1)
C(22) 11511(5) 1599(4) 1032(3) 70(1)
Cl(1) 1787(1) 541(1) 4137(1) 78(1)
Cl(2) 1525(2) 2802(1) 5351(1) 78(1)
C(23) 897(6) 1784(5) 4188(3) 71(1)

B(1)-C(8) 1.571(4) C(14)-H(14) 1
B(1)-C(1) 1.571(4) C(15)-H(15A) 0.98
B(1)-C(3)#1 1.588(4) C(15)-H(15B) 0.98
C(1)-C(1)#1 1.367(5) C(15)-H(15C) 0.98
C(1)-C(2) 1.480(4) C(16)-H(16A) 0.98
C(2)-C(7) 1.381(4) C(16)-H(16B) 0.98
C(2)-C(3) 1.419(3) C(16)-H(16C) 0.98
C(3)-C(4) 1.373(4) C(17)-C(18) 1.512(6)
C(3)-B(1)#1 1.588(4) C(17)-C(19) 1.516(5)
C(4)-C(5) 1.405(4) C(17)-H(17) 1
C(4)-H(4) 0.95 C(18)-H(18A) 0.98
C(5)-C(6) 1.371(4) C(18)-H(18B) 0.98
C(5)-H(5) 0.95 C(18)-H(18C) 0.98
C(6)-C(7) 1.400(4) C(19)-H(19A) 0.98
C(6)-H(6) 0.95 C(19)-H(19B) 0.98
C(7)-H(7) 0.95 C(19)-H(19C) 0.98
C(8)-C(13) 1.400(4) C(20)-C(22) 1.512(5)
C(8)-C(9) 1.405(4) C(20)-C(21) 1.523(5)
C(9)-C(10) 1.395(3) C(20)-H(20) 1
C(9)-C(14) 1.523(4) C(21)-H(21A) 0.98
C(10)-C(11) 1.386(4) C(21)-H(21B) 0.98
C(10)-H(10) 0.95 C(21)-H(21C) 0.98
C(11)-C(12) 1.386(4) C(22)-H(22A) 0.98
C(11)-C(17) 1.525(3) C(22)-H(22B) 0.98
C(12)-C(13) 1.395(3) C(22)-H(22C) 0.98
C(12)-H(12) 0.95 Cl(1)-C(23) 1.720(4)
C(13)-C(20) 1.517(4) Cl(2)-C(23) 1.737(4)
C(14)-C(16) 1.528(4) C(23)-D(23A) 0.99
C(14)-C(15) 1.529(4) C(23)-D(23B) 0.99
170
C(8)-B(1)-C(1) 128.6(2) C(14)-C(15)-H(15C) 109.5
C(8)-B(1)-C(3)#1 129.2(2) H(15A)-C(15)-H(15C) 109.5
C(1)-B(1)-C(3)#1 102.1(2) H(15B)-C(15)-H(15C) 109.5
C(1)#1-C(1)-C(2) 110.9(3) C(14)-C(16)-H(16A) 109.5
C(1)#1-C(1)-B(1) 109.6(3) C(14)-C(16)-H(16B) 109.5
C(2)-C(1)-B(1) 139.5(2) H(16A)-C(16)-H(16B) 109.5
C(7)-C(2)-C(3) 120.6(3) C(14)-C(16)-H(16C) 109.5
C(7)-C(2)-C(1) 129.2(2) H(16A)-C(16)-H(16C) 109.5
C(3)-C(2)-C(1) 110.2(2) H(16B)-C(16)-H(16C) 109.5
C(4)-C(3)-C(2) 119.4(2) C(18)-C(17)-C(19) 110.2(3)
C(4)-C(3)-B(1)#1 133.4(2) C(18)-C(17)-C(11) 110.9(3)
C(2)-C(3)-B(1)#1 107.2(2) C(19)-C(17)-C(11) 113.2(3)
C(3)-C(4)-C(5) 120.1(3) C(18)-C(17)-H(17) 107.4
C(3)-C(4)-H(4) 119.9 C(19)-C(17)-H(17) 107.4
C(5)-C(4)-H(4) 119.9 C(11)-C(17)-H(17) 107.4
C(6)-C(5)-C(4) 120.0(3) C(17)-C(18)-H(18A) 109.5
C(6)-C(5)-H(5) 120 C(17)-C(18)-H(18B) 109.5
C(4)-C(5)-H(5) 120 H(18A)-C(18)-H(18B) 109.5
C(5)-C(6)-C(7) 121.1(3) C(17)-C(18)-H(18C) 109.5
C(5)-C(6)-H(6) 119.5 H(18A)-C(18)-H(18C) 109.5
C(7)-C(6)-H(6) 119.5 H(18B)-C(18)-H(18C) 109.5
C(2)-C(7)-C(6) 118.8(2) C(17)-C(19)-H(19A) 109.5
C(2)-C(7)-H(7) 120.6 C(17)-C(19)-H(19B) 109.5
C(6)-C(7)-H(7) 120.6 H(19A)-C(19)-H(19B) 109.5
C(13)-C(8)-C(9) 119.2(2) C(17)-C(19)-H(19C) 109.5
C(13)-C(8)-B(1) 119.3(2) H(19A)-C(19)-H(19C) 109.5
C(9)-C(8)-B(1) 121.5(2) H(19B)-C(19)-H(19C) 109.5
C(10)-C(9)-C(8) 119.2(2) C(22)-C(20)-C(13) 112.1(3)
C(10)-C(9)-C(14) 121.4(2) C(22)-C(20)-C(21) 111.3(3)
C(8)-C(9)-C(14) 119.4(2) C(13)-C(20)-C(21) 111.9(3)
C(11)-C(10)-C(9) 122.0(2) C(22)-C(20)-H(20) 107.1
C(11)-C(10)-H(10) 119 C(13)-C(20)-H(20) 107.1
C(9)-C(10)-H(10) 119 C(21)-C(20)-H(20) 107.1
C(10)-C(11)-C(12) 118.3(2) C(20)-C(21)-H(21A) 109.5
C(10)-C(11)-C(17) 120.4(2) C(20)-C(21)-H(21B) 109.5
C(12)-C(11)-C(17) 121.4(3) H(21A)-C(21)-H(21B) 109.5
C(11)-C(12)-C(13) 121.3(3) C(20)-C(21)-H(21C) 109.5
C(11)-C(12)-H(12) 119.3 H(21A)-C(21)-H(21C) 109.5
C(13)-C(12)-H(12) 119.3 H(21B)-C(21)-H(21C) 109.5
C(12)-C(13)-C(8) 120.0(2) C(20)-C(22)-H(22A) 109.5
C(12)-C(13)-C(20) 120.6(2) C(20)-C(22)-H(22B) 109.5
C(8)-C(13)-C(20) 119.4(2) H(22A)-C(22)-H(22B) 109.5
C(9)-C(14)-C(16) 113.1(2) C(20)-C(22)-H(22C) 109.5
C(9)-C(14)-C(15) 111.2(2) H(22A)-C(22)-H(22C) 109.5
C(16)-C(14)-C(15) 110.3(2) H(22B)-C(22)-H(22C) 109.5
C(9)-C(14)-H(14) 107.3 Cl(1)-C(23)-Cl(2) 114.5(2)
C(16)-C(14)-H(14) 107.3 Cl(1)-C(23)-D(23A) 108.6
C(15)-C(14)-H(14) 107.3 Cl(2)-C(23)-D(23A) 108.6
C(14)-C(15)-H(15A) 109.5 Cl(1)-C(23)-D(23B) 108.6
C(14)-C(15)-H(15B) 109.5 Cl(2)-C(23)-D(23B) 108.6
H(15A)-C(15)-H(15B) 109.5 D(23A)-C(23)-D(23B) 107.6
171
Empirical formula C44 H58 B2 O2
Space group P 21/c
b = 10.3248(3) Å β = 97.918(2) º
c = 22.3584(7) Å γ = 90 º
Volume 1946.57(11) Å3
Z 2
F(000) 696
Atom x y z U(eq)
O(1) 2505(2) -474(2) 4072(1) 38(1)
C(1) 2698(3) 1903(3) 3987(1) 30(1)
C(2) 3448(3) 2383(3) 3508(1) 33(1)
C(3) 2797(4) 3443(3) 3179(1) 40(1)
C(4) 1436(4) 4063(3) 3311(1) 44(1)
C(5) 738(4) 3600(3) 3793(1) 41(1)
C(6) 1346(3) 2532(3) 4131(1) 32(1)
C(7) 4916(3) 1714(3) 3346(1) 38(1)
C(8) 6116(4) 2627(4) 3123(2) 53(1)
C(9) 4484(4) 625(3) 2894(2) 54(1)
C(10) 778(6) 5215(4) 2933(2) 71(1)
C(11) -179(11) 6087(6) 3202(3) 84(2)
C(12) 315(6) 4921(4) 2289(2) 80(1)
C(10') 778(6) 5215(4) 2933(2) 71(1)
C(11') 1298(19) 6444(11) 3150(5) 84(2)
172
C(12') 315(6) 4921(4) 2289(2) 80(1)
C(13) 515(3) 2026(3) 4645(1) 37(1)
C(14) 145(5) 3079(4) 5081(2) 56(1)
C(15) -963(4) 1256(4) 4402(2) 52(1)
C(16) 4524(3) 518(3) 4917(1) 28(1)
C(17) 4579(3) 1677(3) 5324(1) 31(1)
C(18) 3875(3) 1616(3) 5853(1) 39(1)

O(1)-B(1) 1.353(4) C(12)-H(12A) 0.98
O(1)-H(1) 0.84 C(12)-H(12B) 0.98
C(1)-C(6) 1.398(4) C(12)-H(12C) 0.98
C(1)-C(2) 1.409(4) C(11')-H(11D) 0.98
C(1)-B(1) 1.579(4) C(11')-H(11E) 0.98
C(2)-C(3) 1.390(4) C(11')-H(11F) 0.98
C(2)-C(7) 1.515(4) C(13)-C(14) 1.522(4)
C(3)-C(4) 1.390(4) C(13)-C(15) 1.524(4)
C(3)-H(3) 0.95 C(13)-H(13) 1
C(4)-C(5) 1.386(4) C(14)-H(14A) 0.98
C(4)-C(10) 1.521(4) C(14)-H(14B) 0.98
C(5)-C(6) 1.394(4) C(14)-H(14C) 0.98
C(5)-H(5) 0.95 C(15)-H(15A) 0.98
C(6)-C(13) 1.523(4) C(15)-H(15B) 0.98
C(7)-C(9) 1.523(4) C(15)-H(15C) 0.98
C(7)-C(8) 1.523(4) C(16)-C(16)#1 1.363(5)
C(7)-H(7) 1 C(16)-C(17) 1.500(4)
C(8)-H(8A) 0.98 C(16)-B(1) 1.605(4)
C(8)-H(8B) 0.98 C(17)-C(22) 1.382(4)
C(8)-H(8C) 0.98 C(17)-C(18) 1.400(4)
C(9)-H(9A) 0.98 C(18)-C(19) 1.386(4)
C(9)-H(9B) 0.98 C(18)-H(18) 0.95
C(9)-H(9C) 0.98 C(19)-C(20) 1.369(5)
C(10)-C(11) 1.404(7) C(19)-H(19) 0.95
C(10)-C(12) 1.472(5) C(20)-C(21) 1.381(5)
C(10)-H(10) 1 C(20)-H(20) 0.95
C(11)-H(11A) 0.98 C(21)-C(22) 1.395(4)
C(11)-H(11B) 0.98 C(21)-H(21) 0.95
C(11)-H(11C) 0.98 C(22)-H(22) 0.95

B(1)-O(1)-H(1) 109.5 C(10)-C(12)-H(12B) 109.5
C(6)-C(1)-C(2) 119.0(2) H(12A)-C(12)-H(12B) 109.5
C(6)-C(1)-B(1) 119.5(2) C(10)-C(12)-H(12C) 109.5
C(2)-C(1)-B(1) 121.2(2) H(12A)-C(12)-H(12C) 109.5
C(3)-C(2)-C(1) 119.3(3) H(12B)-C(12)-H(12C) 109.5
C(3)-C(2)-C(7) 120.9(2) H(11D)-C(11')-H(11E) 109.5
C(1)-C(2)-C(7) 119.8(2) H(11D)-C(11')-H(11F) 109.5
C(2)-C(3)-C(4) 122.2(3) H(11E)-C(11')-H(11F) 109.5
C(2)-C(3)-H(3) 118.9 C(14)-C(13)-C(6) 113.4(3)
C(4)-C(3)-H(3) 118.9 C(14)-C(13)-C(15) 111.5(3)
173
C(5)-C(4)-C(3) 117.7(3) C(6)-C(13)-C(15) 110.9(2)
C(5)-C(4)-C(10) 122.5(3) C(14)-C(13)-H(13) 106.9
C(3)-C(4)-C(10) 119.8(3) C(6)-C(13)-H(13) 106.9
C(4)-C(5)-C(6) 121.8(3) C(15)-C(13)-H(13) 106.9
C(4)-C(5)-H(5) 119.1 C(13)-C(14)-H(14A) 109.5
C(6)-C(5)-H(5) 119.1 C(13)-C(14)-H(14B) 109.5
C(5)-C(6)-C(1) 119.9(3) H(14A)-C(14)-H(14B) 109.5
C(5)-C(6)-C(13) 120.2(2) C(13)-C(14)-H(14C) 109.5
C(1)-C(6)-C(13) 119.8(2) H(14A)-C(14)-H(14C) 109.5
C(2)-C(7)-C(9) 111.3(3) H(14B)-C(14)-H(14C) 109.5
C(2)-C(7)-C(8) 114.2(3) C(13)-C(15)-H(15A) 109.5
C(9)-C(7)-C(8) 110.6(3) C(13)-C(15)-H(15B) 109.5
C(2)-C(7)-H(7) 106.8 H(15A)-C(15)-H(15B) 109.5
C(9)-C(7)-H(7) 106.8 C(13)-C(15)-H(15C) 109.5
C(8)-C(7)-H(7) 106.8 H(15A)-C(15)-H(15C) 109.5
C(7)-C(8)-H(8A) 109.5 H(15B)-C(15)-H(15C) 109.5
C(7)-C(8)-H(8B) 109.5 C(16)#1-C(16)-C(17) 119.5(3)
H(8A)-C(8)-H(8B) 109.5 C(16)#1-C(16)-B(1) 125.1(3)
C(7)-C(8)-H(8C) 109.5 C(17)-C(16)-B(1) 115.4(2)
H(8A)-C(8)-H(8C) 109.5 C(22)-C(17)-C(18) 118.3(3)
H(8B)-C(8)-H(8C) 109.5 C(22)-C(17)-C(16) 121.9(2)
C(7)-C(9)-H(9A) 109.5 C(18)-C(17)-C(16) 119.8(2)
C(7)-C(9)-H(9B) 109.5 C(19)-C(18)-C(17) 120.7(3)
H(9A)-C(9)-H(9B) 109.5 C(19)-C(18)-H(18) 119.7
C(7)-C(9)-H(9C) 109.5 C(17)-C(18)-H(18) 119.7
H(9A)-C(9)-H(9C) 109.5 C(20)-C(19)-C(18) 120.3(3)
H(9B)-C(9)-H(9C) 109.5 C(20)-C(19)-H(19) 119.8
C(11)-C(10)-C(12) 117.3(4) C(18)-C(19)-H(19) 119.8
C(11)-C(10)-C(4) 117.0(4) C(19)-C(20)-C(21) 119.9(3)
C(12)-C(10)-C(4) 114.3(3) C(19)-C(20)-H(20) 120.1
C(11)-C(10)-H(10) 101.4 C(21)-C(20)-H(20) 120.1
C(12)-C(10)-H(10) 101.4 C(20)-C(21)-C(22) 120.1(3)
C(4)-C(10)-H(10) 101.4 C(20)-C(21)-H(21) 120
C(10)-C(11)-H(11A) 109.5 C(22)-C(21)-H(21) 120
C(10)-C(11)-H(11B) 109.5 C(17)-C(22)-C(21) 120.7(3)
H(11A)-C(11)-H(11B) 109.5 C(17)-C(22)-H(22) 119.7
C(10)-C(11)-H(11C) 109.5 C(21)-C(22)-H(22) 119.7
H(11A)-C(11)-H(11C) 109.5 O(1)-B(1)-C(1) 114.5(2)
H(11B)-C(11)-H(11C) 109.5 O(1)-B(1)-C(16) 121.6(2)
C(10)-C(12)-H(12A) 109.5 C(1)-B(1)-C(16) 123.9(2)

Empirical formula C66 H88 B2 Cl4 Co
Space group P-1
b = 13.487(2) Å β = 111.343(4) º
c = 14.651(1) Å γ = 95.399(6) º
174
Volume 1890.0(3) Å3
Z 1
F(000) 589
θ range for data collection 3.62 − 68.19 º
Absorption correction Integration
Atom x y z U(eq)
B1 8690(3) 3690(2) 9447(2) 43.4(6)
C1 9922(2) 4441.6(1.8) 9652.7(1.8) 41.7(5)
C10 6368(3) 779(3) 7259(3) 83.7(1.0)
C11 6949(4) 48(2) 7600(4) 91.1(1.2)
C12 8118(3) 499(2) 8511(3) 76.3(9)
C13 8707(3) 1642(2) 9091(2) 54.4(6)
C14 6276(3) 2690(3) 7368(3) 79.4(9)
C15 6439(6) 2527(5) 6331(4) 132.9(1.9)
C16 4880(4) 2554(5) 7194(5) 133(2)
C17 6508(7) -1240(5) 7280(7) 65(2)
C17B 6181(9) -1163(5) 6712(10) 98(2)
C18 6763(10) -1816(10) 6243(8) 89(4)
C18B 5417(12) -1592(7) 7220(9) 98(2)
C19 5012(7) -1584(7) 6761(7) 75(3)
C19B 7148(11) -1840(8) 6556(12) 98(2)
C2 8129(2) 4545.3(1.9) 10143.5(1.9) 43.2(5)
C20 9979(3) 2078(2) 10099(3) 65.0(7)
C21 9776(4) 2069(3) 11064(3) 89.7(1.0)
C22 10977(3) 1453(3) 9928(3) 82.3(1.0)
C23 10851(3) 6248(2) 6567(2) 61.4(7)
C24 10260(3) 4478(2) 3600(2) 58.1(6)
C25 9100(3) 6251(2) 5170(2) 62.7(7)
C26 8651(3) 5518(2) 5527(2) 59.3(7)
C27 9549(3) 3305(2) 4197(3) 66.2(7)
C28 12207(3) 6523(3) 7411(3) 86.3(1.0)
C29 10293(4) 5100(3) 2953(3) 75.8(9)
C3 8994(2) 5619.6(1.8) 10650.2(1.8) 41.9(5)
C30 8266(4) 6534(4) 4290(3) 95.5(1.2)
C31 7279(3) 4901(3) 5110(3) 84(1)
C32 8691(5) 2455(3) 4274(4) 100.3(1.3)
C33 6352(4) 5897(3) 8632(3) 85.9(1.0)
C4 8759(2) 6546(2) 11324(2) 49.5(5)
175
C5 7653(3) 6412(2) 11498(2) 57.6(6)
C6 6800(3) 5367(2) 11000(2) 60.2(7)
C7 7050(2) 4442(2) 10337(2) 51.8(6)
C8 8090(2) 2381.5(1.8) 8761(2) 45.4(5)
C9 6916(3) 1929(2) 7822(2) 60.0(7)
Cl1 6363(3) 5596.7(1.5) 7393.7(1.4) 176.8(9)
Cl2 5528.0(1.1) 6881.9(1.1) 8977.6(1.3) 115.7(4)
Co1 10000 5000 5000 47.11(18)
B1 - C1 1.523(3) C23 - C24 1.418(4)
B1 - C2 1.586(4) C23 - C27 1.420(4)
B1 - C8 1.587(3) C23 - C28 1.499(4)
C1 - C1 1.410(4) C24 - C23 1.418(4)
C1 - C3 1.471(3) C24 - C26 1.427(4)
C10 - C11 1.387(6) C24 - C29 1.492(4)
C10 - H10 0.95 C25 - C26 1.419(4)
C11 - C12 1.373(5) C25 - C27 1.413(5)
C11 - C17 1.594(7) C25 - C30 1.507(4)
C11 - C17B 1.556(8) C26 - C24 1.427(4)
C12 - C13 1.395(4) C26 - C31 1.494(5)
C12 - H12 0.95 C27 - C23 1.420(4)
C13 - C20 1.509(4) C27 - C25 1.413(5)
C14 - C15 1.535(6) C27 - C32 1.508(5)
C14 - C16 1.517(6) C28 - H28A 0.98
C14 - H14 1 C28 - H28B 0.98
C15 - H15A 0.98 C28 - H28C 0.98
C15 - H15B 0.98 C29 - H29A 0.98
C15 - H15C 0.98 C29 - H29B 0.98
C16 - H16A 0.98 C29 - H29C 0.98
C16 - H16B 0.98 C3 - C1 1.470(3)
C16 - H16C 0.98 C3 - C4 1.389(3)
C17 - C18 1.572(11) C30 - H30A 0.98
C17 - C19 1.547(10) C30 - H30B 0.98
C17 - H17A 1 C30 - H30C 0.98
C17B - C18B 1.540(11) C31 - H31A 0.98
C17B - C19B 1.531(11) C31 - H31B 0.98
C17B - H17B 1 C31 - H31C 0.98
C18 - H18A 0.98 C32 - H32A 0.98
C18 - H18B 0.98 C32 - H32B 0.98
C18 - H18C 0.98 C32 - H32C 0.98
C18B - H18D 0.98 C33 - H33A 0.99
C18B - H18E 0.98 C33 - H33B 0.99
C18B - H18F 0.98 C4 - C5 1.397(4)
C19 - H19A 0.98 C4 - H4 0.95
C19 - H19B 0.98 C5 - C6 1.386(4)
C19 - H19C 0.98 C5 - H5 0.95
C19B - H19D 0.98 C6 - C7 1.391(4)
C19B - H19E 0.98 C6 - H6 0.95
C19B - H19F 0.98 C7 - H7 0.95
C2 - C3 1.420(3) C8 - C13 1.408(4)
C2 - C7 1.379(4) C8 - C9 1.395(4)
C20 - C21 1.521(5) C9 - C10 1.396(4)
C20 - C22 1.526(4) C9 - C14 1.531(4)
176
C20 - H20 1 Cl1 - C33 1.707(4)
C21 - H21A 0.98 Cl2 - C33 1.732(4)
C21 - H21B 0.98 Co1 - C23 2.045(3)
C21 - H21C 0.98 Co1 - C24 2.045(3)
C22 - H22A 0.98 Co1 - C25 2.046(3)
C22 - H22B 0.98 Co1 - C26 2.043(3)
C22 - H22C 0.98 Co1 - C27 2.041(3)

C1 - B1 - C2 102.33(19) C25 - Co1 - C25 179.998(1)
C1 - B1 - C8 131.1(2) C26 - C24 - C29 125.9(3)
C1 - C1 - B1 110.8(3) C26 - C24 - Co1 69.49(15)
C1 - C1 - C3 109.0(2) C26 - C25 - C30 125.6(3)
C10 - C11 - C17 134.9(4) C26 - C25 - Co1 69.60(15)
C10 - C11 - C17B 108.6(6) C26 - C31 - H31A 109.5
C10 - C9 - C14 120.0(3) C26 - C31 - H31B 109.5
C11 - C10 - C9 122.3(3) C26 - C31 - H31C 109.5
C11 - C10 - H10 118.9 C26 - Co1 - C23 111.44(12)
C11 - C12 - C13 122.4(3) C26 - Co1 - C24 40.87(11)
C11 - C12 - H12 118.8 C26 - Co1 - C25 139.39(12)
C11 - C17 - H17A 114.8 C26 - Co1 - C26 179.998(1)
C11 - C17B - H17B 111.4 C27 - C23 - C28 125.5(3)
C12 - C11 - C10 117.2(3) C27 - C23 - Co1 69.52(16)
C12 - C11 - C17 107.3(4) C27 - C25 - C26 108.3(2)
C12 - C11 - C17B 133.4(5) C27 - C25 - C30 126.0(3)
C12 - C13 - C20 119.3(3) C27 - C25 - Co1 69.61(16)
C12 - C13 - C8 120.0(3) C27 - C32 - H32A 109.5
C13 - C12 - H12 118.8 C27 - C32 - H32B 109.5
C13 - C20 - C21 110.8(3) C27 - C32 - H32C 109.5
C13 - C20 - C22 113.5(3) C27 - Co1 - C23 139.32(12)
C13 - C20 - H20 107.4 C27 - Co1 - C24 68.33(12)
C13 - C8 - B1 121.3(2) C27 - Co1 - C25 139.56(13)
C14 - C15 - H15A 109.5 C27 - Co1 - C26 68.40(12)
C14 - C15 - H15B 109.5 C27 - Co1 - C27 180
C14 - C15 - H15C 109.5 C28 - C23 - Co1 127.2(2)
C14 - C16 - H16A 109.5 C29 - C24 - Co1 127.9(2)
C14 - C16 - H16B 109.5 C3 - C1 - B1 140.3(2)
C14 - C16 - H16C 109.5 C3 - C2 - B1 107.6(2)
C15 - C14 - H14 107 C3 - C4 - C5 119.2(2)
C16 - C14 - C15 112.9(4) C3 - C4 - H4 120.4
C16 - C14 - C9 113.0(3) C30 - C25 - Co1 128.0(2)
C16 - C14 - H14 107 C31 - C26 - Co1 128.4(2)
C17 - C18 - H18A 109.5 C32 - C27 - Co1 128.5(2)
C17 - C18 - H18B 109.5 C4 - C3 - C1 128.8(2)
C17 - C18 - H18C 109.5 C4 - C3 - C2 120.8(2)
C17 - C19 - H19A 109.5 C4 - C5 - H5 119.9
C17 - C19 - H19B 109.5 C5 - C4 - H4 120.4
C17 - C19 - H19C 109.5 C5 - C6 - C7 120.3(2)
C17B - C11 - C17 30.5(4) C5 - C6 - H6 119.9
C17B - C18B - H18D 109.5 C6 - C5 - C4 120.2(2)
C17B - C18B - H18E 109.5 C6 - C5 - H5 119.9
177
C17B - C18B - H18F 109.5 C6 - C7 - H7 119.5
C17B - C19B - H19D 109.5 C7 - C2 - B1 133.9(2)
C17B - C19B - H19E 109.5 C7 - C2 - C3 118.5(2)
C17B - C19B - H19F 109.5 C7 - C6 - H6 119.9
C18 - C17 - C11 102.7(7) C8 - C13 - C20 120.6(2)
C18 - C17 - H17A 114.8 C8 - C9 - C10 120.1(3)
C18B - C17B - C11 103.8(8) C8 - C9 - C14 119.8(2)
C18B - C17B - H17B 111.4 C9 - C10 - H10 118.9
C19 - C17 - C11 106.9(6) C9 - C14 - C15 109.6(3)
C19 - C17 - C18 101.2(8) C9 - C14 - H14 107
C19 - C17 - H17A 114.8 C9 - C8 - B1 120.8(2)
C19B - C17B - C11 108.5(8) C9 - C8 - C13 117.9(2)
C19B - C17B - C18B 110.0(11) Cl1 - C33 - Cl2 112.7(2)
C19B - C17B - H17B 111.4 Cl1 - C33 - H33A 109.1
C2 - B1 - C8 126.6(2) Cl1 - C33 - H33B 109.1
C2 - C3 - C1 110.3(2) Cl2 - C33 - H33A 109.1
C2 - C7 - C6 121.0(2) Cl2 - C33 - H33B 109.1
C2 - C7 - H7 119.5 H15A - C15 - H15B 109.5
C20 - C21 - H21A 109.5 H15A - C15 - H15C 109.5
C20 - C21 - H21B 109.5 H15B - C15 - H15C 109.5
C20 - C21 - H21C 109.5 H16A - C16 - H16B 109.5
C20 - C22 - H22A 109.5 H16A - C16 - H16C 109.5
C20 - C22 - H22B 109.5 H16B - C16 - H16C 109.5
C20 - C22 - H22C 109.5 H18A - C18 - H18B 109.5
C21 - C20 - C22 110.0(3) H18A - C18 - H18C 109.5
C21 - C20 - H20 107.4 H18B - C18 - H18C 109.5
C22 - C20 - H20 107.4 H18D - C18B - H18E 109.5
C23 - C24 - C26 108.0(2) H18D - C18B - H18F 109.5
C23 - C24 - C29 126.1(3) H18E - C18B - H18F 109.5
C23 - C24 - Co1 69.71(15) H19A - C19 - H19B 109.5
C23 - C27 - C32 125.8(3) H19A - C19 - H19C 109.5
C23 - C27 - Co1 69.80(15) H19B - C19 - H19C 109.5
C23 - C28 - H28A 109.5 H19D - C19B - H19E 109.5
C23 - C28 - H28B 109.5 H19D - C19B - H19F 109.5
C23 - C28 - H28C 109.5 H19E - C19B - H19F 109.5
C23 - Co1 - C23 180.00(19) H21A - C21 - H21B 109.5
C23 - Co1 - C24 139.41(12) H21A - C21 - H21C 109.5
C23 - Co1 - C25 68.24(12) H21B - C21 - H21C 109.5
C24 - C23 - C27 107.9(3) H22A - C22 - H22B 109.5
C24 - C23 - C28 126.6(3) H22A - C22 - H22C 109.5
C24 - C23 - Co1 69.70(15) H22B - C22 - H22C 109.5
C24 - C26 - C31 126.0(3) H28A - C28 - H28B 109.5
C24 - C26 - Co1 69.64(16) H28A - C28 - H28C 109.5
C24 - C29 - H29A 109.5 H28B - C28 - H28C 109.5
C24 - C29 - H29B 109.5 H29A - C29 - H29B 109.5
C24 - C29 - H29C 109.5 H29A - C29 - H29C 109.5
C24 - Co1 - C23 40.59(12) H29B - C29 - H29C 109.5
C24 - Co1 - C24 180.00(7) H30A - C30 - H30B 109.5
C24 - Co1 - C25 111.70(11) H30A - C30 - H30C 109.5
C25 - C26 - C24 107.6(3) H30B - C30 - H30C 109.5
C25 - C26 - C31 126.3(3) H31A - C31 - H31B 109.5
C25 - C26 - Co1 69.80(16) H31A - C31 - H31C 109.5
C25 - C27 - C23 108.2(3) H31B - C31 - H31C 109.5
C25 - C27 - C32 126.0(3) H32A - C32 - H32B 109.5
178
C25 - C27 - Co1 69.95(16) H32A - C32 - H32C 109.5
C25 - C30 - H30A 109.5 H32B - C32 - H32C 109.5
C25 - C30 - H30B 109.5 H33A - C33 - H33B 107.8
C25 - C30 - H30C 109.5

Empirical formula C76 H118 B2 K2 O8
Crystal system Orthorhombic
Space group Pbca
b = 19.9550(4) Å β = 90 º
c = 22.8279(5) Å γ = 90 º
Volume 7358.5(3) Å3
Z 4
F(000) 2744
Atom x y z U(eq)
K(1) 3361(1) 9469(1) 171(1) 57(1)
O(1) 2859(1) 8540(1) 964(1) 72(1)
O(2) 2287(2) 10482(1) 68(1) 82(1)
O(3) 2405(2) 8650(1) -458(1) 81(1)
B(1) 4774(2) 10413(1) 843(1) 43(1)
C(1) 4928(1) 10266(1) 206(1) 41(1)
C(2) 4894(1) 10997(1) 74(1) 42(1)
C(3) 4995(2) 11456(1) -371(1) 46(1)
C(4) 4918(2) 12146(1) -220(1) 54(1)
C(5) 4752(2) 12343(1) 337(1) 60(1)
C(6) 4652(2) 11869(1) 794(1) 58(1)
C(7) 4730(1) 11203(1) 666(1) 47(1)
C(8) 4706(2) 10040(1) 1458(1) 45(1)
C(9) 5355(2) 9641(1) 1684(1) 51(1)
179
C(10) 5291(2) 9364(2) 2244(1) 67(1)
C(11) 4612(2) 9464(2) 2597(1) 76(1)
C(12) 3974(2) 9850(2) 2377(1) 68(1)
C(13) 4006(2) 10135(1) 1817(1) 51(1)
C(14) 6149(2) 9553(1) 1338(1) 58(1)
C(15) 6618(3) 8908(2) 1469(2) 99(1)
C(16) 6713(2) 10158(2) 1423(1) 70(1)
C(17) 4411(5) 9339(4) 3267(3) 60(1)
C(18) 5108(17) 9620(20) 3640(20) 84(2)
C(19) 4405(6) 8579(4) 3296(3) 85(2)
C(17') 4705(3) 9075(3) 3182(2) 60(1)
C(18') 5045(13) 9569(17) 3628(17) 84(2)
C(19') 3873(4) 8819(4) 3390(3) 85(2)
C(20) 3270(2) 10541(1) 1609(1) 56(1)
C(21) 2464(2) 10138(2) 1616(1) 64(1)
C(22) 3168(2) 11183(2) 1966(2) 84(1)
C(23) 3317(2) 8302(2) 1456(2) 74(1)
C(24) 2688(3) 8153(2) 1921(2) 96(1)
C(25) 1894(3) 8141(2) 1625(2) 105(1)
C(26) 2059(2) 8241(2) 996(2) 89(1)
C(27) 2427(3) 11189(2) 114(2) 95(1)
C(28) 1686(3) 11462(2) 381(3) 123(2)
C(29) 996(3) 10974(2) 257(2) 97(1)
C(30) 1425(3) 10358(2) 56(2) 94(1)
C(31) 2889(4) 8076(3) -517(3) 143(2)
C(32) 2753(4) 7782(3) -1053(3) 138(2)
C(33) 2002(5) 8090(3) -1294(2) 141(2)
C(34) 1727(2) 8595(2) -844(2) 89(1)
O(4) 5129(3) 1833(4) 3258(2) 219(3)
C(35) 5028(4) 2277(3) 2776(3) 131(2)
C(36) 5594(6) 1977(5) 2318(3) 231(6)
C(37) 5727(5) 1307(4) 2569(3) 182(4)
C(38) 5782(7) 1389(5) 3183(3) 228(5)

K(1)-O(3) 2.667(2) C(17')-C(18') 1.521(5)
K(1)-O(2) 2.675(2) C(17')-H(17') 1
K(1)-O(1) 2.714(2) C(18')-H(18D) 0.98
K(1)-C(1)#1 2.943(2) C(18')-H(18E) 0.98
K(1)-C(1) 2.991(2) C(18')-H(18F) 0.98
K(1)-C(2)#1 3.021(2) C(19')-H(19D) 0.98
K(1)-C(3)#1 3.266(2) C(19')-H(19E) 0.98
K(1)-C(31) 3.282(5) C(19')-H(19F) 0.98
K(1)-B(1) 3.333(3) C(20)-C(22) 1.528(4)
O(1)-C(26) 1.426(4) C(20)-C(21) 1.531(4)
O(1)-C(23) 1.427(4) C(20)-H(20) 1
O(2)-C(30) 1.414(5) C(21)-H(21A) 0.98
O(2)-C(27) 1.432(5) C(21)-H(21B) 0.98
O(3)-C(31) 1.394(5) C(21)-H(21C) 0.98
O(3)-C(34) 1.410(4) C(22)-H(22A) 0.98
B(1)-C(1) 1.504(3) C(22)-H(22B) 0.98
180
B(1)-C(8) 1.592(3) C(22)-H(22C) 0.98
B(1)-C(7) 1.629(4) C(23)-C(24) 1.500(5)
C(1)-C(1)#1 1.437(4) C(23)-H(23A) 0.99
C(1)-C(2) 1.492(3) C(23)-H(23B) 0.99
C(1)-K(1)#1 2.943(2) C(24)-C(25) 1.450(6)
C(2)-C(3) 1.376(3) C(24)-H(24A) 0.99
C(2)-C(7) 1.437(3) C(24)-H(24B) 0.99
C(2)-K(1)#1 3.021(2) C(25)-C(26) 1.475(6)
C(3)-C(4) 1.426(3) C(25)-H(25A) 0.99
C(3)-K(1)#1 3.266(2) C(25)-H(25B) 0.99
C(3)-H(3) 0.95 C(26)-H(26A) 0.99
C(4)-C(5) 1.358(4) C(26)-H(26B) 0.99
C(4)-H(4) 0.95 C(27)-C(28) 1.450(6)
C(5)-C(6) 1.416(4) C(27)-H(27A) 0.99
C(5)-H(5) 0.95 C(27)-H(27B) 0.99
C(6)-C(7) 1.367(4) C(28)-C(29) 1.506(7)
C(6)-H(6) 0.95 C(28)-H(28A) 0.99
C(8)-C(13) 1.410(3) C(28)-H(28B) 0.99
C(8)-C(9) 1.415(4) C(29)-C(30) 1.484(6)
C(9)-C(10) 1.396(4) C(29)-H(29A) 0.99
C(9)-C(14) 1.516(4) C(29)-H(29B) 0.99
C(10)-C(11) 1.376(5) C(30)-H(30A) 0.99
C(10)-H(10) 0.95 C(30)-H(30B) 0.99
C(11)-C(12) 1.381(5) C(31)-C(32) 1.376(7)
C(11)-C(17') 1.552(6) C(31)-H(31A) 0.99
C(11)-C(17) 1.584(8) C(31)-H(31B) 0.99
C(12)-C(13) 1.400(3) C(32)-C(33) 1.465(8)
C(12)-H(12) 0.95 C(32)-H(32A) 0.99
C(13)-C(20) 1.514(4) C(32)-H(32B) 0.99
C(14)-C(15) 1.523(4) C(33)-C(34) 1.506(7)
C(14)-C(16) 1.523(4) C(33)-H(33A) 0.99
C(14)-H(14) 1 C(33)-H(33B) 0.99
C(15)-H(15A) 0.98 C(34)-H(34A) 0.99
C(15)-H(15B) 0.98 C(34)-H(34B) 0.99
C(15)-H(15C) 0.98 O(4)-C(38) 1.389(6)
C(16)-H(16A) 0.98 O(4)-C(35) 1.422(5)
C(16)-H(16B) 0.98 C(35)-C(36) 1.513(7)
C(16)-H(16C) 0.98 C(35)-H(35A) 0.99
C(17)-C(19) 1.517(5) C(35)-H(35B) 0.99
C(17)-C(18) 1.521(5) C(36)-C(37) 1.472(7)
C(17)-H(17) 1 C(36)-H(36A) 0.99
C(18)-H(18A) 0.98 C(36)-H(36B) 0.99
C(18)-H(18B) 0.98 C(37)-C(38) 1.413(7)
C(18)-H(18C) 0.98 C(37)-H(37A) 0.99
C(19)-H(19A) 0.98 C(37)-H(37B) 0.99
C(19)-H(19B) 0.98 C(38)-H(38A) 0.99
C(19)-H(19C) 0.98 C(38)-H(38B) 0.99
C(17')-C(19') 1.513(4)

O(3)-K(1)-O(2) 92.30(8) C(18')-C(17')-H(17') 110.1
O(3)-K(1)-O(1) 76.56(7) C(11)-C(17')-H(17') 110.1
181
O(2)-K(1)-O(1) 112.40(8) C(17')-C(18')-H(18D) 109.5
O(3)-K(1)-C(1)#1 119.77(8) C(17')-C(18')-H(18E) 109.5
O(2)-K(1)-C(1)#1 116.56(8) H(18D)-C(18')-H(18E) 109.5
O(1)-K(1)-C(1)#1 126.79(7) C(17')-C(18')-H(18F) 109.5
O(3)-K(1)-C(1) 146.11(8) H(18D)-C(18')-H(18F) 109.5
O(2)-K(1)-C(1) 98.58(7) H(18E)-C(18')-H(18F) 109.5
O(1)-K(1)-C(1) 126.76(6) C(17')-C(19')-H(19D) 109.5
C(1)#1-K(1)-C(1) 28.00(8) C(17')-C(19')-H(19E) 109.5
O(3)-K(1)-C(2)#1 104.62(7) H(19D)-C(19')-H(19E) 109.5
O(2)-K(1)-C(2)#1 145.25(7) C(17')-C(19')-H(19F) 109.5
O(1)-K(1)-C(2)#1 101.08(7) H(19D)-C(19')-H(19F) 109.5
C(1)#1-K(1)-C(2)#1 28.93(6) H(19E)-C(19')-H(19F) 109.5
C(1)-K(1)-C(2)#1 51.58(6) C(13)-C(20)-C(22) 111.5(3)
O(3)-K(1)-C(3)#1 101.54(7) C(13)-C(20)-C(21) 112.5(2)
O(2)-K(1)-C(3)#1 165.20(8) C(22)-C(20)-C(21) 110.1(2)
O(1)-K(1)-C(3)#1 76.37(6) C(13)-C(20)-H(20) 107.5
C(1)#1-K(1)-C(3)#1 51.60(6) C(22)-C(20)-H(20) 107.5
C(1)-K(1)-C(3)#1 66.94(6) C(21)-C(20)-H(20) 107.5
C(2)#1-K(1)-C(3)#1 24.89(6) C(20)-C(21)-H(21A) 109.5
O(3)-K(1)-C(31) 24.41(10) C(20)-C(21)-H(21B) 109.5
O(2)-K(1)-C(31) 116.59(11) H(21A)-C(21)-H(21B) 109.5
O(1)-K(1)-C(31) 70.81(15) C(20)-C(21)-H(21C) 109.5
C(1)#1-K(1)-C(31) 103.33(14) H(21A)-C(21)-H(21C) 109.5
C(1)-K(1)-C(31) 131.27(15) H(21B)-C(21)-H(21C) 109.5
C(2)#1-K(1)-C(31) 82.39(13) C(20)-C(22)-H(22A) 109.5
C(3)#1-K(1)-C(31) 77.13(10) C(20)-C(22)-H(22B) 109.5
O(3)-K(1)-B(1) 172.00(8) H(22A)-C(22)-H(22B) 109.5
O(2)-K(1)-B(1) 93.26(8) C(20)-C(22)-H(22C) 109.5
O(1)-K(1)-B(1) 106.50(6) H(22A)-C(22)-H(22C) 109.5
C(1)#1-K(1)-B(1) 52.40(6) H(22B)-C(22)-H(22C) 109.5
C(1)-K(1)-B(1) 26.82(6) O(1)-C(23)-C(24) 105.8(3)
C(2)#1-K(1)-B(1) 67.68(6) O(1)-C(23)-H(23A) 110.6
C(3)#1-K(1)-B(1) 72.45(6) C(24)-C(23)-H(23A) 110.6
C(31)-K(1)-B(1) 149.08(11) O(1)-C(23)-H(23B) 110.6
C(26)-O(1)-C(23) 106.9(3) C(24)-C(23)-H(23B) 110.6
C(26)-O(1)-K(1) 126.2(2) H(23A)-C(23)-H(23B) 108.7
C(23)-O(1)-K(1) 126.70(17) C(25)-C(24)-C(23) 105.8(3)
C(30)-O(2)-C(27) 109.3(3) C(25)-C(24)-H(24A) 110.6
C(30)-O(2)-K(1) 120.5(2) C(23)-C(24)-H(24A) 110.6
C(27)-O(2)-K(1) 129.5(2) C(25)-C(24)-H(24B) 110.6
C(31)-O(3)-C(34) 108.2(3) C(23)-C(24)-H(24B) 110.6
C(31)-O(3)-K(1) 103.3(2) H(24A)-C(24)-H(24B) 108.7
C(34)-O(3)-K(1) 146.5(2) C(24)-C(25)-C(26) 107.0(3)
C(1)-B(1)-C(8) 140.5(2) C(24)-C(25)-H(25A) 110.3
C(1)-B(1)-C(7) 87.49(17) C(26)-C(25)-H(25A) 110.3
C(8)-B(1)-C(7) 131.9(2) C(24)-C(25)-H(25B) 110.3
C(1)-B(1)-K(1) 63.81(12) C(26)-C(25)-H(25B) 110.3
C(8)-B(1)-K(1) 95.41(13) H(25A)-C(25)-H(25B) 108.6
C(7)-B(1)-K(1) 113.79(14) O(1)-C(26)-C(25) 105.7(3)
C(1)#1-C(1)-C(2) 126.6(2) O(1)-C(26)-H(26A) 110.6
C(1)#1-C(1)-B(1) 143.5(3) C(25)-C(26)-H(26A) 110.6
C(2)-C(1)-B(1) 89.91(18) O(1)-C(26)-H(26B) 110.6
C(1)#1-C(1)-K(1)#1 77.86(17) C(25)-C(26)-H(26B) 110.6
C(2)-C(1)-K(1)#1 78.44(12) H(26A)-C(26)-H(26B) 108.7
182
B(1)-C(1)-K(1)#1 113.81(15) O(2)-C(27)-C(28) 105.7(4)
C(1)#1-C(1)-K(1) 74.14(17) O(2)-C(27)-H(27A) 110.6
C(2)-C(1)-K(1) 118.90(14) C(28)-C(27)-H(27A) 110.6
B(1)-C(1)-K(1) 89.37(13) O(2)-C(27)-H(27B) 110.6
K(1)#1-C(1)-K(1) 152.00(8) C(28)-C(27)-H(27B) 110.6
C(3)-C(2)-C(7) 121.7(2) H(27A)-C(27)-H(27B) 108.7
C(3)-C(2)-C(1) 142.7(2) C(27)-C(28)-C(29) 106.8(4)
C(7)-C(2)-C(1) 95.51(18) C(27)-C(28)-H(28A) 110.4
C(3)-C(2)-K(1)#1 87.54(14) C(29)-C(28)-H(28A) 110.4
C(7)-C(2)-K(1)#1 115.70(14) C(27)-C(28)-H(28B) 110.4
C(1)-C(2)-K(1)#1 72.62(12) C(29)-C(28)-H(28B) 110.4
C(2)-C(3)-C(4) 117.0(2) H(28A)-C(28)-H(28B) 108.6
C(2)-C(3)-K(1)#1 67.57(13) C(30)-C(29)-C(28) 104.4(4)
C(4)-C(3)-K(1)#1 125.69(17) C(30)-C(29)-H(29A) 110.9
C(2)-C(3)-H(3) 121.5 C(28)-C(29)-H(29A) 110.9
C(4)-C(3)-H(3) 121.5 C(30)-C(29)-H(29B) 110.9
K(1)#1-C(3)-H(3) 78.9 C(28)-C(29)-H(29B) 110.9
C(5)-C(4)-C(3) 121.4(2) H(29A)-C(29)-H(29B) 108.9
C(5)-C(4)-H(4) 119.3 O(2)-C(30)-C(29) 107.9(4)
C(3)-C(4)-H(4) 119.3 O(2)-C(30)-H(30A) 110.1
C(4)-C(5)-C(6) 121.4(2) C(29)-C(30)-H(30A) 110.1
C(4)-C(5)-H(5) 119.3 O(2)-C(30)-H(30B) 110.1
C(6)-C(5)-H(5) 119.3 C(29)-C(30)-H(30B) 110.1
C(7)-C(6)-C(5) 118.7(2) H(30A)-C(30)-H(30B) 108.4
C(7)-C(6)-H(6) 120.7 C(32)-C(31)-O(3) 110.3(4)
C(5)-C(6)-H(6) 120.7 C(32)-C(31)-K(1) 145.5(5)
C(6)-C(7)-C(2) 119.8(2) O(3)-C(31)-K(1) 52.26(19)
C(6)-C(7)-B(1) 153.1(2) C(32)-C(31)-H(31A) 109.6
C(2)-C(7)-B(1) 87.07(18) O(3)-C(31)-H(31A) 109.6
C(13)-C(8)-C(9) 117.3(2) K(1)-C(31)-H(31A) 61.9
C(13)-C(8)-B(1) 120.3(2) C(32)-C(31)-H(31B) 109.6
C(9)-C(8)-B(1) 122.3(2) O(3)-C(31)-H(31B) 109.6
C(10)-C(9)-C(8) 120.1(3) K(1)-C(31)-H(31B) 104.7
C(10)-C(9)-C(14) 119.6(3) H(31A)-C(31)-H(31B) 108.1
C(8)-C(9)-C(14) 120.2(2) C(31)-C(32)-C(33) 106.7(4)
C(11)-C(10)-C(9) 122.6(3) C(31)-C(32)-H(32A) 110.4
C(11)-C(10)-H(10) 118.7 C(33)-C(32)-H(32A) 110.4
C(9)-C(10)-H(10) 118.7 C(31)-C(32)-H(32B) 110.4
C(10)-C(11)-C(12) 117.5(2) C(33)-C(32)-H(32B) 110.4
C(10)-C(11)-C(17') 110.8(3) H(32A)-C(32)-H(32B) 108.6
C(12)-C(11)-C(17') 131.7(3) C(32)-C(33)-C(34) 105.7(4)
C(10)-C(11)-C(17) 134.9(4) C(32)-C(33)-H(33A) 110.6
C(12)-C(11)-C(17) 106.7(4) C(34)-C(33)-H(33A) 110.6
C(17')-C(11)-C(17) 27.1(3) C(32)-C(33)-H(33B) 110.6
C(11)-C(12)-C(13) 122.1(3) C(34)-C(33)-H(33B) 110.6
C(11)-C(12)-H(12) 118.9 H(33A)-C(33)-H(33B) 108.7
C(13)-C(12)-H(12) 118.9 O(3)-C(34)-C(33) 104.4(4)
C(12)-C(13)-C(8) 120.4(3) O(3)-C(34)-H(34A) 110.9
C(12)-C(13)-C(20) 118.3(2) C(33)-C(34)-H(34A) 110.9
C(8)-C(13)-C(20) 121.3(2) O(3)-C(34)-H(34B) 110.9
C(9)-C(14)-C(15) 114.6(3) C(33)-C(34)-H(34B) 110.9
C(9)-C(14)-C(16) 110.3(2) H(34A)-C(34)-H(34B) 108.9
C(15)-C(14)-C(16) 110.3(3) C(38)-O(4)-C(35) 113.0(5)
C(9)-C(14)-H(14) 107.1 O(4)-C(35)-C(36) 102.6(5)
183
C(15)-C(14)-H(14) 107.1 O(4)-C(35)-H(35A) 111.2
C(16)-C(14)-H(14) 107.1 C(36)-C(35)-H(35A) 111.2
C(14)-C(15)-H(15A) 109.5 O(4)-C(35)-H(35B) 111.2
C(14)-C(15)-H(15B) 109.5 C(36)-C(35)-H(35B) 111.2
H(15A)-C(15)-H(15B) 109.5 H(35A)-C(35)-H(35B) 109.2
C(14)-C(15)-H(15C) 109.5 C(37)-C(36)-C(35) 100.3(5)
H(15A)-C(15)-H(15C) 109.5 C(37)-C(36)-H(36A) 111.7
H(15B)-C(15)-H(15C) 109.5 C(35)-C(36)-H(36A) 111.7
C(14)-C(16)-H(16A) 109.5 C(37)-C(36)-H(36B) 111.7
C(14)-C(16)-H(16B) 109.5 C(35)-C(36)-H(36B) 111.7
H(16A)-C(16)-H(16B) 109.5 H(36A)-C(36)-H(36B) 109.5
C(14)-C(16)-H(16C) 109.5 C(38)-C(37)-C(36) 106.9(6)
H(16A)-C(16)-H(16C) 109.5 C(38)-C(37)-H(37A) 110.3
H(16B)-C(16)-H(16C) 109.5 C(36)-C(37)-H(37A) 110.3
C(19)-C(17)-C(18) 111(2) C(38)-C(37)-H(37B) 110.3
C(19)-C(17)-C(11) 101.6(5) C(36)-C(37)-H(37B) 110.3
C(18)-C(17)-C(11) 109(3) H(37A)-C(37)-H(37B) 108.6
C(19)-C(17)-H(17) 111.6 O(4)-C(38)-C(37) 98.5(7)
C(18)-C(17)-H(17) 111.6 O(4)-C(38)-H(38A) 112.1
C(11)-C(17)-H(17) 111.6 C(37)-C(38)-H(38A) 112.1
C(19')-C(17')-C(18') 109.2(15) O(4)-C(38)-H(38B) 112.1
C(19')-C(17')-C(11) 110.7(4) C(37)-C(38)-H(38B) 112.1
C(18')-C(17')-C(11) 107(2) H(38A)-C(38)-H(38B) 109.7
C(19')-C(17')-H(17') 110.1

Empirical formula C30 H43 B K N2 O2
Space group P 21/c
b = 14.6667(2) Å β = 02.0051(10) º
c = 19.3119(4) Å γ = 90 º
Volume 2857.13(9) Å3
Z 4
F(000) 1052
Crystal size 0.26 x 0.24 x 0.14 mm
Reflections collected / unique 23720
Independent reflections 6559 [R(int) = 0.0356]
184
Atom x y z U(eq)
K(1) 6855(1) 5951(1) 962(1) 36(1)
O(1) 9110(2) 6566(1) 728(1) 48(1)
O(2) 6545(2) 6369(2) 2240(1) 62(1)
C(1) 5498(2) 4648(2) -14(1) 35(1)
C(2) 6159(2) 4934(2) -589(1) 34(1)
C(3) 5621(2) 5753(2) -905(1) 37(1)
C(4) 6144(3) 6106(2) -1443(1) 41(1)
C(5) 7184(3) 5669(2) -1674(1) 41(1)
C(6) 7724(2) 4863(2) -1371(1) 40(1)
C(7) 7216(2) 4478(2) -825(1) 39(1)
C(8) 6439(2) 3041(2) 727(1) 32(1)
C(9) 6330(2) 2243(1) 303(1) 30(1)
C(10) 7068(2) 1470(1) 541(1) 29(1)
C(11) 7952(2) 1449(1) 1192(1) 29(1)
C(12) 8078(2) 2232(2) 1600(1) 30(1)
C(13) 7346(2) 3018(1) 1378(1) 30(1)
C(14) 5338(2) 2224(2) -401(1) 35(1)
C(15) 3947(2) 2056(2) -274(1) 40(1)
C(16) 5650(3) 1536(2) -934(1) 49(1)
C(17) 8744(2) 601(2) 1448(1) 35(1)
C(18) 9642(3) 322(2) 956(2) 52(1)
C(19) 7850(3) -187(2) 1554(2) 48(1)
C(20) 7596(2) 3870(2) 1836(1) 35(1)
C(21) 8871(3) 4334(2) 1738(2) 54(1)
C(22) 7611(4) 3695(2) 2615(2) 60(1)
C(23) 9320(3) 6353(2) 37(2) 46(1)
C(24) 9879(3) 7205(2) -240(2) 54(1)
C(25) 9976(4) 7881(2) 345(2) 76(1)
C(26) 9934(3) 7321(2) 990(2) 56(1)
C(27) 5251(3) 6332(3) 2394(2) 78(1)
C(28) 5404(3) 6086(3) 3135(2) 71(1)
C(29) 6824(3) 6297(3) 3470(2) 64(1)
C(30) 7413(3) 6622(3) 2868(2) 59(1)
B(1) 5523(3) 3928(2) 524(1) 33(1)

K(1)-O(1) 2.6198(19) C(15)-H(15A) 0.98
K(1)-O(2) 2.626(2) C(15)-H(15B) 0.98
K(1)-C(1) 2.841(2) C(15)-H(15C) 0.98
K(1)-C(1)#1 2.857(2) C(16)-H(16A) 0.98
K(1)-C(15)#1 3.246(3) C(16)-H(16B) 0.98
K(1)-C(2) 3.289(2) C(16)-H(16C) 0.98
K(1)-B(1) 3.305(3) C(17)-C(18) 1.515(4)
185
K(1)-C(2)#1 3.307(2) C(17)-C(19) 1.519(4)
K(1)-B(1)#1 3.370(3) C(17)-H(17) 1
K(1)-C(23) 3.449(3) C(18)-H(18A) 0.98
K(1)-C(20) 3.494(2) C(18)-H(18B) 0.98
K(1)-C(14)#1 3.527(2) C(18)-H(18C) 0.98
O(1)-C(26) 1.423(3) C(19)-H(19A) 0.98
O(1)-C(23) 1.431(3) C(19)-H(19B) 0.98
O(2)-C(30) 1.400(4) C(19)-H(19C) 0.98
O(2)-C(27) 1.428(4) C(20)-C(22) 1.523(4)
C(1)-C(1)#1 1.466(4) C(20)-C(21) 1.526(4)
C(1)-C(2) 1.479(3) C(20)-H(20) 1
C(1)-B(1) 1.479(3) C(21)-H(21A) 0.98
C(1)-K(1)#1 2.857(2) C(21)-H(21B) 0.98
C(2)-C(3) 1.408(4) C(21)-H(21C) 0.98
C(2)-C(7) 1.433(3) C(22)-H(22A) 0.98
C(2)-K(1)#1 3.307(2) C(22)-H(22B) 0.98
C(3)-C(4) 1.368(3) C(22)-H(22C) 0.98
C(3)-B(1)#1 1.585(4) C(23)-C(24) 1.519(4)
C(4)-C(5) 1.400(3) C(23)-H(23A) 0.99
C(4)-H(4) 0.95 C(23)-H(23B) 0.99
C(5)-C(6) 1.384(4) C(24)-C(25) 1.490(4)
C(5)-H(5) 0.95 C(24)-H(24A) 0.99
C(6)-C(7) 1.390(3) C(24)-H(24B) 0.99
C(6)-H(6) 0.95 C(25)-C(26) 1.499(5)
C(7)-H(7) 0.95 C(25)-H(25A) 0.99
C(8)-C(13) 1.403(3) C(25)-H(25B) 0.99
C(8)-C(9) 1.419(3) C(26)-H(26A) 0.99
C(8)-B(1) 1.608(3) C(26)-H(26B) 0.99
C(9)-C(10) 1.390(3) C(27)-C(28) 1.451(5)
C(9)-C(14) 1.523(3) C(27)-H(27A) 0.99
C(10)-C(11) 1.391(3) C(27)-H(27B) 0.99
C(10)-H(10) 0.95 C(28)-C(29) 1.506(5)
C(11)-C(12) 1.385(3) C(28)-H(28A) 0.99
C(11)-C(17) 1.514(3) C(28)-H(28B) 0.99
C(12)-C(13) 1.395(3) C(29)-C(30) 1.497(5)
C(12)-H(12) 0.95 C(29)-H(29A) 0.99
C(13)-C(20) 1.522(3) C(29)-H(29B) 0.99
C(14)-C(16) 1.522(3) C(30)-H(30A) 0.99
C(14)-C(15) 1.525(3) C(30)-H(30B) 0.99
C(14)-K(1)#1 3.527(2) B(1)-C(3)#1 1.585(4)
C(14)-H(14) 1 B(1)-K(1)#1 3.370(3)

O(1)-K(1)-O(2) 111.57(6) C(16)-C(14)-C(9) 114.7(2)
O(1)-K(1)-C(1) 116.73(7) C(16)-C(14)-C(15) 109.9(2)
O(2)-K(1)-C(1) 129.90(7) C(9)-C(14)-C(15) 109.81(19)
O(1)-K(1)-C(1)#1 131.43(7) C(16)-C(14)-K(1)#1 120.53(15)
O(2)-K(1)-C(1)#1 114.85(7) C(9)-C(14)-K(1)#1 121.94(14)
C(1)-K(1)-C(1)#1 29.82(9) C(15)-C(14)-K(1)#1 66.87(12)
O(1)-K(1)-C(15)#1 77.24(6) C(16)-C(14)-H(14) 107.4
O(2)-K(1)-C(15)#1 95.94(8) C(9)-C(14)-H(14) 107.4
C(1)-K(1)-C(15)#1 106.60(6) C(15)-C(14)-H(14) 107.4
186
C(1)#1-K(1)-C(15)#1 84.51(6) K(1)#1-C(14)-H(14) 40.5
O(1)-K(1)-C(2) 91.87(6) C(14)-C(15)-H(15A) 109.5
O(2)-K(1)-C(2) 156.28(6) C(14)-C(15)-H(15B) 109.5
C(1)-K(1)-C(2) 26.66(6) H(15A)-C(15)-H(15B) 109.5
C(1)#1-K(1)-C(2) 44.10(6) C(14)-C(15)-H(15C) 109.5
C(15)#1-K(1)-C(2) 92.68(6) H(15A)-C(15)-H(15C) 109.5
O(1)-K(1)-B(1) 127.01(7) H(15B)-C(15)-H(15C) 109.5
O(2)-K(1)-B(1) 108.95(7) C(14)-C(16)-H(16A) 109.5
C(1)-K(1)-B(1) 26.49(6) C(14)-C(16)-H(16B) 109.5
C(1)#1-K(1)-B(1) 46.18(6) H(16A)-C(16)-H(16B) 109.5
C(15)#1-K(1)-B(1) 130.29(6) C(14)-C(16)-H(16C) 109.5
C(2)-K(1)-B(1) 50.18(6) H(16A)-C(16)-H(16C) 109.5
O(1)-K(1)-C(2)#1 157.76(6) H(16B)-C(16)-H(16C) 109.5
O(2)-K(1)-C(2)#1 90.21(6) C(11)-C(17)-C(18) 112.0(2)
C(1)-K(1)-C(2)#1 43.96(6) C(11)-C(17)-C(19) 111.57(19)
C(1)#1-K(1)-C(2)#1 26.49(6) C(18)-C(17)-C(19) 110.3(2)
C(15)#1-K(1)-C(2)#1 96.68(6) C(11)-C(17)-H(17) 107.6
C(2)-K(1)-C(2)#1 66.82(6) C(18)-C(17)-H(17) 107.6
B(1)-K(1)-C(2)#1 43.10(6) C(19)-C(17)-H(17) 107.6
O(1)-K(1)-B(1)#1 110.48(6) C(17)-C(18)-H(18A) 109.5
O(2)-K(1)-B(1)#1 125.35(7) C(17)-C(18)-H(18B) 109.5
C(1)-K(1)-B(1)#1 45.51(6) H(18A)-C(18)-H(18B) 109.5
C(1)#1-K(1)-B(1)#1 25.83(6) C(17)-C(18)-H(18C) 109.5
C(15)#1-K(1)-B(1)#1 61.68(6) H(18A)-C(18)-H(18C) 109.5
C(2)-K(1)-B(1)#1 42.76(6) H(18B)-C(18)-H(18C) 109.5
B(1)-K(1)-B(1)#1 68.85(7) C(17)-C(19)-H(19A) 109.5
C(2)#1-K(1)-B(1)#1 49.50(6) C(17)-C(19)-H(19B) 109.5
O(1)-K(1)-C(23) 22.37(6) H(19A)-C(19)-H(19B) 109.5
O(2)-K(1)-C(23) 133.93(6) C(17)-C(19)-H(19C) 109.5
C(1)-K(1)-C(23) 94.93(7) H(19A)-C(19)-H(19C) 109.5
C(1)#1-K(1)-C(23) 109.90(7) H(19B)-C(19)-H(19C) 109.5
C(15)#1-K(1)-C(23) 77.66(7) C(13)-C(20)-C(22) 113.6(2)
C(2)-K(1)-C(23) 69.55(6) C(13)-C(20)-C(21) 109.9(2)
B(1)-K(1)-C(23) 109.47(6) C(22)-C(20)-C(21) 111.4(2)
C(2)#1-K(1)-C(23) 135.66(6) C(13)-C(20)-K(1) 116.30(14)
B(1)#1-K(1)-C(23) 91.95(7) C(22)-C(20)-K(1) 125.49(16)
O(1)-K(1)-C(20) 105.73(6) C(21)-C(20)-K(1) 70.05(15)
O(2)-K(1)-C(20) 78.90(7) C(13)-C(20)-H(20) 107.2
C(1)-K(1)-C(20) 76.18(6) C(22)-C(20)-H(20) 107.2
C(1)#1-K(1)-C(20) 96.45(6) C(21)-C(20)-H(20) 107.2
C(15)#1-K(1)-C(20) 174.69(6) K(1)-C(20)-H(20) 37.4
C(2)-K(1)-C(20) 91.62(6) C(20)-C(21)-H(21A) 109.5
B(1)-K(1)-C(20) 51.47(6) C(20)-C(21)-H(21B) 109.5
C(2)#1-K(1)-C(20) 82.17(6) H(21A)-C(21)-H(21B) 109.5
B(1)#1-K(1)-C(20) 120.32(6) C(20)-C(21)-H(21C) 109.5
C(23)-K(1)-C(20) 106.80(7) H(21A)-C(21)-H(21C) 109.5
O(1)-K(1)-C(14)#1 102.78(6) H(21B)-C(21)-H(21C) 109.5
O(2)-K(1)-C(14)#1 85.14(7) C(20)-C(22)-H(22A) 109.5
C(1)-K(1)-C(14)#1 96.36(6) C(20)-C(22)-H(22B) 109.5
C(1)#1-K(1)-C(14)#1 68.38(6) H(22A)-C(22)-H(22B) 109.5
C(15)#1-K(1)-C(14)#1 25.60(6) C(20)-C(22)-H(22C) 109.5
C(2)-K(1)-C(14)#1 93.43(6) H(22A)-C(22)-H(22C) 109.5
B(1)-K(1)-C(14)#1 113.38(6) H(22B)-C(22)-H(22C) 109.5
C(2)#1-K(1)-C(14)#1 73.58(6) O(1)-C(23)-C(24) 106.9(2)
187
B(1)#1-K(1)-C(14)#1 52.54(6) O(1)-C(23)-K(1) 44.18(11)
C(23)-K(1)-C(14)#1 101.87(6) C(24)-C(23)-K(1) 134.23(19)
C(20)-K(1)-C(14)#1 150.84(6) O(1)-C(23)-H(23A) 110.3
C(26)-O(1)-C(23) 107.8(2) C(24)-C(23)-H(23A) 110.3
C(26)-O(1)-K(1) 133.86(17) K(1)-C(23)-H(23A) 68
C(23)-O(1)-K(1) 113.45(14) O(1)-C(23)-H(23B) 110.3
C(30)-O(2)-C(27) 106.6(2) C(24)-C(23)-H(23B) 110.3
C(30)-O(2)-K(1) 134.07(17) K(1)-C(23)-H(23B) 113.2
C(27)-O(2)-K(1) 119.31(18) H(23A)-C(23)-H(23B) 108.6
C(1)#1-C(1)-C(2) 105.3(2) C(25)-C(24)-C(23) 104.5(2)
C(1)#1-C(1)-B(1) 112.7(3) C(25)-C(24)-H(24A) 110.9
C(2)-C(1)-B(1) 141.9(2) C(23)-C(24)-H(24A) 110.9
C(1)#1-C(1)-K(1) 75.69(17) C(25)-C(24)-H(24B) 110.9
C(2)-C(1)-K(1) 93.81(13) C(23)-C(24)-H(24B) 110.9
B(1)-C(1)-K(1) 94.54(14) H(24A)-C(24)-H(24B) 108.9
C(1)#1-C(1)-K(1)#1 74.49(16) C(24)-C(25)-C(26) 104.9(3)
C(2)-C(1)-K(1)#1 93.99(13) C(24)-C(25)-H(25A) 110.8
B(1)-C(1)-K(1)#1 96.86(14) C(26)-C(25)-H(25A) 110.8
K(1)-C(1)-K(1)#1 150.18(9) C(24)-C(25)-H(25B) 110.8
C(3)-C(2)-C(7) 121.2(2) C(26)-C(25)-H(25B) 110.8
C(3)-C(2)-C(1) 111.5(2) H(25A)-C(25)-H(25B) 108.8
C(7)-C(2)-C(1) 127.4(2) O(1)-C(26)-C(25) 104.5(2)
C(3)-C(2)-K(1) 90.01(14) O(1)-C(26)-H(26A) 110.9
C(7)-C(2)-K(1) 117.76(14) C(25)-C(26)-H(26A) 110.9
C(1)-C(2)-K(1) 59.53(11) O(1)-C(26)-H(26B) 110.9
C(3)-C(2)-K(1)#1 88.43(13) C(25)-C(26)-H(26B) 110.9
C(7)-C(2)-K(1)#1 119.37(15) H(26A)-C(26)-H(26B) 108.9
C(1)-C(2)-K(1)#1 59.51(11) O(2)-C(27)-C(28) 107.5(3)
K(1)-C(2)-K(1)#1 113.18(6) O(2)-C(27)-H(27A) 110.2
C(4)-C(3)-C(2) 118.1(2) C(28)-C(27)-H(27A) 110.2
C(4)-C(3)-B(1)#1 133.6(2) O(2)-C(27)-H(27B) 110.2
C(2)-C(3)-B(1)#1 108.3(2) C(28)-C(27)-H(27B) 110.2
C(3)-C(4)-C(5) 121.2(3) H(27A)-C(27)-H(27B) 108.5
C(3)-C(4)-H(4) 119.4 C(27)-C(28)-C(29) 105.6(3)
C(5)-C(4)-H(4) 119.4 C(27)-C(28)-H(28A) 110.6
C(6)-C(5)-C(4) 121.6(2) C(29)-C(28)-H(28A) 110.6
C(6)-C(5)-H(5) 119.2 C(27)-C(28)-H(28B) 110.6
C(4)-C(5)-H(5) 119.2 C(29)-C(28)-H(28B) 110.6
C(5)-C(6)-C(7) 119.1(2) H(28A)-C(28)-H(28B) 108.7
C(5)-C(6)-H(6) 120.4 C(30)-C(29)-C(28) 104.3(3)
C(7)-C(6)-H(6) 120.4 C(30)-C(29)-H(29A) 110.9
C(6)-C(7)-C(2) 118.9(2) C(28)-C(29)-H(29A) 110.9
C(6)-C(7)-H(7) 120.6 C(30)-C(29)-H(29B) 110.9
C(2)-C(7)-H(7) 120.6 C(28)-C(29)-H(29B) 110.9
C(13)-C(8)-C(9) 117.06(19) H(29A)-C(29)-H(29B) 108.9
C(13)-C(8)-B(1) 119.10(19) O(2)-C(30)-C(29) 107.4(2)
C(9)-C(8)-B(1) 123.71(19) O(2)-C(30)-H(30A) 110.2
C(10)-C(9)-C(8) 120.71(19) C(29)-C(30)-H(30A) 110.2
C(10)-C(9)-C(14) 119.98(19) O(2)-C(30)-H(30B) 110.2
C(8)-C(9)-C(14) 119.23(19) C(29)-C(30)-H(30B) 110.2
C(9)-C(10)-C(11) 121.8(2) H(30A)-C(30)-H(30B) 108.5
C(9)-C(10)-H(10) 119.1 C(1)-B(1)-C(3)#1 102.2(2)
C(11)-C(10)-H(10) 119.1 C(1)-B(1)-C(8) 132.3(2)
C(12)-C(11)-C(10) 117.57(19) C(3)#1-B(1)-C(8) 125.6(2)
188
C(12)-C(11)-C(17) 121.00(19) C(1)-B(1)-K(1) 58.97(12)
C(10)-C(11)-C(17) 121.43(19) C(3)#1-B(1)-K(1) 85.78(13)
C(11)-C(12)-C(13) 121.97(19) C(8)-B(1)-K(1) 118.18(14)
C(11)-C(12)-H(12) 119 C(1)-B(1)-K(1)#1 57.32(12)
C(13)-C(12)-H(12) 119 C(3)#1-B(1)-K(1)#1 84.26(13)
C(12)-C(13)-C(8) 120.8(2) C(8)-B(1)-K(1)#1 122.46(14)
C(12)-C(13)-C(20) 118.96(19) K(1)-B(1)-K(1)#1 111.15(7)
C(8)-C(13)-C(20) 120.12(19) C(16)-C(14)-C(9) 114.7(2)
O(1)-K(1)-O(2) 111.57(6) C(16)-C(14)-C(15) 109.9(2)
O(1)-K(1)-C(1) 116.73(7) C(9)-C(14)-C(15) 109.81(19)
O(2)-K(1)-C(1) 129.90(7) C(16)-C(14)-K(1)#1 120.53(15)
O(1)-K(1)-C(1)#1 131.43(7) C(9)-C(14)-K(1)#1 121.94(14)
O(2)-K(1)-C(1)#1 114.85(7) C(15)-C(14)-K(1)#1 66.87(12)
C(1)-K(1)-C(1)#1 29.82(9) C(16)-C(14)-H(14) 107.4
O(1)-K(1)-C(15)#1 77.24(6) C(9)-C(14)-H(14) 107.4
O(2)-K(1)-C(15)#1 95.94(8) C(15)-C(14)-H(14) 107.4
C(1)-K(1)-C(15)#1 106.60(6) K(1)#1-C(14)-H(14) 40.5
C(1)#1-K(1)-C(15)#1 84.51(6) C(14)-C(15)-H(15A) 109.5
O(1)-K(1)-C(2) 91.87(6) C(14)-C(15)-H(15B) 109.5
O(2)-K(1)-C(2) 156.28(6) H(15A)-C(15)-H(15B) 109.5
C(1)-K(1)-C(2) 26.66(6) C(14)-C(15)-H(15C) 109.5
C(1)#1-K(1)-C(2) 44.10(6) H(15A)-C(15)-H(15C) 109.5
C(15)#1-K(1)-C(2) 92.68(6) H(15B)-C(15)-H(15C) 109.5
O(1)-K(1)-B(1) 127.01(7) C(14)-C(16)-H(16A) 109.5
O(2)-K(1)-B(1) 108.95(7) C(14)-C(16)-H(16B) 109.5
C(1)-K(1)-B(1) 26.49(6) H(16A)-C(16)-H(16B) 109.5
C(1)#1-K(1)-B(1) 46.18(6) C(14)-C(16)-H(16C) 109.5
C(15)#1-K(1)-B(1) 130.29(6) H(16A)-C(16)-H(16C) 109.5
C(2)-K(1)-B(1) 50.18(6) H(16B)-C(16)-H(16C) 109.5
O(1)-K(1)-C(2)#1 157.76(6) C(11)-C(17)-C(18) 112.0(2)
O(2)-K(1)-C(2)#1 90.21(6) C(11)-C(17)-C(19) 111.57(19)
C(1)-K(1)-C(2)#1 43.96(6) C(18)-C(17)-C(19) 110.3(2)
C(1)#1-K(1)-C(2)#1 26.49(6) C(11)-C(17)-H(17) 107.6
C(15)#1-K(1)-C(2)#1 96.68(6) C(18)-C(17)-H(17) 107.6
C(2)-K(1)-C(2)#1 66.82(6) C(19)-C(17)-H(17) 107.6
B(1)-K(1)-C(2)#1 43.10(6) C(17)-C(18)-H(18A) 109.5
O(1)-K(1)-B(1)#1 110.48(6) C(17)-C(18)-H(18B) 109.5
O(2)-K(1)-B(1)#1 125.35(7) H(18A)-C(18)-H(18B) 109.5
C(1)-K(1)-B(1)#1 45.51(6) C(17)-C(18)-H(18C) 109.5
C(1)#1-K(1)-B(1)#1 25.83(6) H(18A)-C(18)-H(18C) 109.5
C(15)#1-K(1)-B(1)#1 61.68(6) H(18B)-C(18)-H(18C) 109.5
C(2)-K(1)-B(1)#1 42.76(6) C(17)-C(19)-H(19A) 109.5
B(1)-K(1)-B(1)#1 68.85(7) C(17)-C(19)-H(19B) 109.5
C(2)#1-K(1)-B(1)#1 49.50(6) H(19A)-C(19)-H(19B) 109.5
O(1)-K(1)-C(23) 22.37(6) C(17)-C(19)-H(19C) 109.5
O(2)-K(1)-C(23) 133.93(6) H(19A)-C(19)-H(19C) 109.5
C(1)-K(1)-C(23) 94.93(7) H(19B)-C(19)-H(19C) 109.5
C(1)#1-K(1)-C(23) 109.90(7) C(13)-C(20)-C(22) 113.6(2)
C(15)#1-K(1)-C(23) 77.66(7) C(13)-C(20)-C(21) 109.9(2)
C(2)-K(1)-C(23) 69.55(6) C(22)-C(20)-C(21) 111.4(2)
B(1)-K(1)-C(23) 109.47(6) C(13)-C(20)-K(1) 116.30(14)
C(2)#1-K(1)-C(23) 135.66(6) C(22)-C(20)-K(1) 125.49(16)
B(1)#1-K(1)-C(23) 91.95(7) C(21)-C(20)-K(1) 70.05(15)
O(1)-K(1)-C(20) 105.73(6) C(13)-C(20)-H(20) 107.2
189
O(2)-K(1)-C(20) 78.90(7) C(22)-C(20)-H(20) 107.2
C(1)-K(1)-C(20) 76.18(6) C(21)-C(20)-H(20) 107.2
C(1)#1-K(1)-C(20) 96.45(6) K(1)-C(20)-H(20) 37.4
C(15)#1-K(1)-C(20) 174.69(6) C(20)-C(21)-H(21A) 109.5
C(2)-K(1)-C(20) 91.62(6) C(20)-C(21)-H(21B) 109.5
B(1)-K(1)-C(20) 51.47(6) H(21A)-C(21)-H(21B) 109.5
C(2)#1-K(1)-C(20) 82.17(6) C(20)-C(21)-H(21C) 109.5
B(1)#1-K(1)-C(20) 120.32(6) H(21A)-C(21)-H(21C) 109.5
C(23)-K(1)-C(20) 106.80(7) H(21B)-C(21)-H(21C) 109.5
O(1)-K(1)-C(14)#1 102.78(6) C(20)-C(22)-H(22A) 109.5
O(2)-K(1)-C(14)#1 85.14(7) C(20)-C(22)-H(22B) 109.5
C(1)-K(1)-C(14)#1 96.36(6) H(22A)-C(22)-H(22B) 109.5
C(1)#1-K(1)-C(14)#1 68.38(6) C(20)-C(22)-H(22C) 109.5
C(15)#1-K(1)-C(14)#1 25.60(6) H(22A)-C(22)-H(22C) 109.5
C(2)-K(1)-C(14)#1 93.43(6) H(22B)-C(22)-H(22C) 109.5
B(1)-K(1)-C(14)#1 113.38(6) O(1)-C(23)-C(24) 106.9(2)
C(2)#1-K(1)-C(14)#1 73.58(6) O(1)-C(23)-K(1) 44.18(11)
B(1)#1-K(1)-C(14)#1 52.54(6) C(24)-C(23)-K(1) 134.23(19)
C(23)-K(1)-C(14)#1 101.87(6) O(1)-C(23)-H(23A) 110.3
C(20)-K(1)-C(14)#1 150.84(6) C(24)-C(23)-H(23A) 110.3
C(26)-O(1)-C(23) 107.8(2) K(1)-C(23)-H(23A) 68
C(26)-O(1)-K(1) 133.86(17) O(1)-C(23)-H(23B) 110.3
C(23)-O(1)-K(1) 113.45(14) C(24)-C(23)-H(23B) 110.3
C(30)-O(2)-C(27) 106.6(2) K(1)-C(23)-H(23B) 113.2
C(30)-O(2)-K(1) 134.07(17) H(23A)-C(23)-H(23B) 108.6
C(27)-O(2)-K(1) 119.31(18) C(25)-C(24)-C(23) 104.5(2)
C(1)#1-C(1)-C(2) 105.3(2) C(25)-C(24)-H(24A) 110.9
C(1)#1-C(1)-B(1) 112.7(3) C(23)-C(24)-H(24A) 110.9
C(2)-C(1)-B(1) 141.9(2) C(25)-C(24)-H(24B) 110.9
C(1)#1-C(1)-K(1) 75.69(17) C(23)-C(24)-H(24B) 110.9
C(2)-C(1)-K(1) 93.81(13) H(24A)-C(24)-H(24B) 108.9
B(1)-C(1)-K(1) 94.54(14) C(24)-C(25)-C(26) 104.9(3)
C(1)#1-C(1)-K(1)#1 74.49(16) C(24)-C(25)-H(25A) 110.8
C(2)-C(1)-K(1)#1 93.99(13) C(26)-C(25)-H(25A) 110.8
B(1)-C(1)-K(1)#1 96.86(14) C(24)-C(25)-H(25B) 110.8
K(1)-C(1)-K(1)#1 150.18(9) C(26)-C(25)-H(25B) 110.8
C(3)-C(2)-C(7) 121.2(2) H(25A)-C(25)-H(25B) 108.8
C(3)-C(2)-C(1) 111.5(2) O(1)-C(26)-C(25) 104.5(2)
C(7)-C(2)-C(1) 127.4(2) O(1)-C(26)-H(26A) 110.9
C(3)-C(2)-K(1) 90.01(14) C(25)-C(26)-H(26A) 110.9
C(7)-C(2)-K(1) 117.76(14) O(1)-C(26)-H(26B) 110.9
C(1)-C(2)-K(1) 59.53(11) C(25)-C(26)-H(26B) 110.9
C(3)-C(2)-K(1)#1 88.43(13) H(26A)-C(26)-H(26B) 108.9
C(7)-C(2)-K(1)#1 119.37(15) O(2)-C(27)-C(28) 107.5(3)
C(1)-C(2)-K(1)#1 59.51(11) O(2)-C(27)-H(27A) 110.2
K(1)-C(2)-K(1)#1 113.18(6) C(28)-C(27)-H(27A) 110.2
C(4)-C(3)-C(2) 118.1(2) O(2)-C(27)-H(27B) 110.2
C(4)-C(3)-B(1)#1 133.6(2) C(28)-C(27)-H(27B) 110.2
C(2)-C(3)-B(1)#1 108.3(2) H(27A)-C(27)-H(27B) 108.5
C(3)-C(4)-C(5) 121.2(3) C(27)-C(28)-C(29) 105.6(3)
C(3)-C(4)-H(4) 119.4 C(27)-C(28)-H(28A) 110.6
C(5)-C(4)-H(4) 119.4 C(29)-C(28)-H(28A) 110.6
C(6)-C(5)-C(4) 121.6(2) C(27)-C(28)-H(28B) 110.6
C(6)-C(5)-H(5) 119.2 C(29)-C(28)-H(28B) 110.6
190
C(4)-C(5)-H(5) 119.2 H(28A)-C(28)-H(28B) 108.7
C(5)-C(6)-C(7) 119.1(2) C(30)-C(29)-C(28) 104.3(3)
C(5)-C(6)-H(6) 120.4 C(30)-C(29)-H(29A) 110.9
C(7)-C(6)-H(6) 120.4 C(28)-C(29)-H(29A) 110.9
C(6)-C(7)-C(2) 118.9(2) C(30)-C(29)-H(29B) 110.9
C(6)-C(7)-H(7) 120.6 C(28)-C(29)-H(29B) 110.9
C(2)-C(7)-H(7) 120.6 H(29A)-C(29)-H(29B) 108.9
C(13)-C(8)-C(9) 117.06(19) O(2)-C(30)-C(29) 107.4(2)
C(13)-C(8)-B(1) 119.10(19) O(2)-C(30)-H(30A) 110.2
C(9)-C(8)-B(1) 123.71(19) C(29)-C(30)-H(30A) 110.2
C(10)-C(9)-C(8) 120.71(19) O(2)-C(30)-H(30B) 110.2
C(10)-C(9)-C(14) 119.98(19) C(29)-C(30)-H(30B) 110.2
C(8)-C(9)-C(14) 119.23(19) H(30A)-C(30)-H(30B) 108.5
C(9)-C(10)-C(11) 121.8(2) C(1)-B(1)-C(3)#1 102.2(2)
C(9)-C(10)-H(10) 119.1 C(1)-B(1)-C(8) 132.3(2)
C(11)-C(10)-H(10) 119.1 C(3)#1-B(1)-C(8) 125.6(2)
C(12)-C(11)-C(10) 117.57(19) C(1)-B(1)-K(1) 58.97(12)
C(12)-C(11)-C(17) 121.00(19) C(3)#1-B(1)-K(1) 85.78(13)
C(10)-C(11)-C(17) 121.43(19) C(8)-B(1)-K(1) 118.18(14)
C(11)-C(12)-C(13) 121.97(19) C(1)-B(1)-K(1)#1 57.32(12)
C(11)-C(12)-H(12) 119 C(3)#1-B(1)-K(1)#1 84.26(13)
C(13)-C(12)-H(12) 119 C(8)-B(1)-K(1)#1 122.46(14)
C(12)-C(13)-C(8) 120.8(2) K(1)-B(1)-K(1)#1 111.15(7)
C(12)-C(13)-C(20) 118.96(19)

Empirical formula C44 H56 B2
Space group P -1
b = 11.9746(7) Å β = 85.920(3) º
c = 13.9071(6) Å γ = 88.345(2) º
Volume 1869.97(18) Å3
Z 2
F(000) 660
θ range for data collection 2.13 to 27.29º
191
Atom x y z U(eq)
C(1) 4206(4) 6999(4) 518(3) 33(1)
C(2) 4246(4) 7806(4) -440(3) 34(1)
C(3) 3743(4) 8915(4) -170(3) 32(1)
C(4) 3264(4) 8859(4) 781(3) 33(1)
C(5) 2749(4) 9815(4) 1124(3) 42(1)
C(6) 2725(4) 10813(4) 522(4) 45(1)
C(7) 3198(4) 10852(4) -424(4) 45(1)
C(8) 3723(4) 9914(4) -780(3) 39(1)
C(9) 3652(4) 5948(4) 288(3) 33(1)
C(10) 3225(4) 6035(4) -633(3) 31(1)
C(11) 2658(4) 5121(4) -927(3) 41(1)
C(12) 2558(4) 4138(4) -304(4) 45(1)
C(13) 2990(5) 4065(4) 598(4) 44(1)
C(14) 3540(4) 4946(4) 906(3) 40(1)
C(15) 3111(4) 7126(3) 2348(3) 30(1)
C(16) 2007(4) 6669(4) 2600(3) 36(1)
C(17) 1776(4) 6099(4) 3520(3) 43(1)
C(18) 2609(4) 5989(4) 4200(3) 36(1)
C(19) 3693(4) 6477(4) 3953(3) 36(1)
C(20) 3949(4) 7059(4) 3038(3) 34(1)
C(21) 1066(4) 6791(5) 1877(4) 50(1)
C(22) 451(5) 5705(5) 1785(4) 63(2)
C(23) 152(5) 7688(5) 2113(5) 80(2)
C(24) 2372(5) 5358(4) 5200(3) 50(1)
C(25) 1738(5) 4253(4) 5193(4) 56(2)
C(26) 1718(6) 6085(5) 5882(4) 74(2)
C(27) 5130(4) 7613(4) 2798(3) 38(1)
C(28) 5264(5) 8579(5) 3396(4) 64(2)
C(29) 6164(5) 6818(5) 2878(4) 64(2)
C(30) 3166(4) 7816(4) -2163(3) 33(1)
C(31) 2048(4) 8307(4) -2268(3) 37(1)
C(32) 1834(4) 8959(4) -3143(3) 41(1)
C(33) 2683(4) 9117(4) -3901(3) 38(1)
C(34) 3767(4) 8591(4) -3788(3) 35(1)
C(35) 4026(4) 7930(3) -2934(3) 31(1)
C(36) 1100(4) 8146(5) -1464(4) 50(1)
C(37) 574(5) 9237(5) -1156(5) 72(2)
C(38) 136(6) 7407(5) -1707(5) 87(2)
C(39) 2452(5) 9836(4) -4850(3) 49(1)
C(40) 1812(5) 10934(5) -4689(4) 65(2)
C(41) 1817(6) 9194(5) -5507(4) 69(2)
C(42) 5208(4) 7347(4) -2838(3) 36(1)
C(43) 6219(5) 8143(5) -2929(4) 66(2)
C(44) 5412(5) 6469(5) -3535(4) 66(2)
B(1) 3468(4) 7658(5) 1296(4) 33(1)
B(2) 3506(4) 7224(5) -1155(4) 33(1)
192
C(1)-C(9) 1.500(6) C(25)-H(25B) 0.98
C(1)-C(2) 1.551(6) C(25)-H(25C) 0.98
C(1)-B(1) 1.589(7) C(26)-H(26A) 0.98
C(1)-H(1) 1 C(26)-H(26B) 0.98
C(2)-C(3) 1.508(6) C(26)-H(26C) 0.98
C(2)-B(2) 1.579(7) C(27)-C(29) 1.490(7)
C(2)-H(2) 1 C(27)-C(28) 1.518(7)
C(3)-C(8) 1.384(6) C(27)-H(27) 1
C(3)-C(4) 1.388(6) C(28)-H(28A) 0.98
C(4)-C(5) 1.388(6) C(28)-H(28B) 0.98
C(4)-B(1) 1.548(7) C(28)-H(28C) 0.98
C(5)-C(6) 1.378(6) C(29)-H(29A) 0.98
C(5)-H(5) 0.95 C(29)-H(29B) 0.98
C(6)-C(7) 1.382(6) C(29)-H(29C) 0.98
C(6)-H(6) 0.95 C(30)-C(31) 1.392(6)
C(7)-C(8) 1.382(6) C(30)-C(35) 1.395(6)
C(7)-H(7) 0.95 C(30)-B(2) 1.563(6)
C(8)-H(8) 0.95 C(31)-C(32) 1.399(6)
C(9)-C(10) 1.392(6) C(31)-C(36) 1.495(6)
C(9)-C(14) 1.396(6) C(32)-C(33) 1.377(6)
C(10)-C(11) 1.399(6) C(32)-H(32) 0.95
C(10)-B(2) 1.553(7) C(33)-C(34) 1.375(6)
C(11)-C(12) 1.381(6) C(33)-C(39) 1.524(6)
C(11)-H(11) 0.95 C(34)-C(35) 1.393(6)
C(12)-C(13) 1.372(7) C(34)-H(34) 0.95
C(12)-H(12) 0.95 C(35)-C(42) 1.500(6)
C(13)-C(14) 1.365(6) C(36)-C(38) 1.506(8)
C(13)-H(13) 0.95 C(36)-C(37) 1.515(7)
C(14)-H(14) 0.95 C(36)-H(36) 1
C(15)-C(16) 1.386(6) C(37)-H(37A) 0.98
C(15)-C(20) 1.392(6) C(37)-H(37B) 0.98
C(15)-B(1) 1.557(6) C(37)-H(37C) 0.98
C(16)-C(17) 1.390(6) C(38)-H(38A) 0.98
C(16)-C(21) 1.510(6) C(38)-H(38B) 0.98
C(17)-C(18) 1.376(6) C(38)-H(38C) 0.98
C(17)-H(17) 0.95 C(39)-C(41) 1.494(7)
C(18)-C(19) 1.380(6) C(39)-C(40) 1.515(7)
C(18)-C(24) 1.513(6) C(39)-H(39) 1
C(19)-C(20) 1.393(6) C(40)-H(40A) 0.98
C(19)-H(19) 0.95 C(40)-H(40B) 0.98
C(20)-C(27) 1.510(6) C(40)-H(40C) 0.98
C(21)-C(22) 1.516(7) C(41)-H(41A) 0.98
C(21)-C(23) 1.519(8) C(41)-H(41B) 0.98
C(21)-H(21) 1 C(41)-H(41C) 0.98
C(22)-H(22A) 0.98 C(42)-C(43) 1.501(7)
C(22)-H(22B) 0.98 C(42)-C(44) 1.514(6)
C(22)-H(22C) 0.98 C(42)-H(42) 1
C(23)-H(23A) 0.98 C(43)-H(43A) 0.98
C(23)-H(23B) 0.98 C(43)-H(43B) 0.98
C(23)-H(23C) 0.98 C(43)-H(43C) 0.98
C(24)-C(26) 1.505(7) C(44)-H(44A) 0.98
193
C(24)-C(25) 1.525(7) C(44)-H(44B) 0.98
C(24)-H(24) 1 C(44)-H(44C) 0.98
C(25)-H(25A) 0.98

C(9)-C(1)-C(2) 105.4(3) C(24)-C(26)-H(26C) 109.5
C(9)-C(1)-B(1) 115.2(4) H(26A)-C(26)-H(26C) 109.5
C(2)-C(1)-B(1) 105.5(4) H(26B)-C(26)-H(26C) 109.5
C(9)-C(1)-H(1) 110.2 C(29)-C(27)-C(20) 114.0(4)
C(2)-C(1)-H(1) 110.2 C(29)-C(27)-C(28) 110.8(5)
B(1)-C(1)-H(1) 110.2 C(20)-C(27)-C(28) 111.4(4)
C(3)-C(2)-C(1) 105.7(3) C(29)-C(27)-H(27) 106.7
C(3)-C(2)-B(2) 115.1(4) C(20)-C(27)-H(27) 106.7
C(1)-C(2)-B(2) 105.7(4) C(28)-C(27)-H(27) 106.7
C(3)-C(2)-H(2) 110 C(27)-C(28)-H(28A) 109.5
C(1)-C(2)-H(2) 110 C(27)-C(28)-H(28B) 109.5
B(2)-C(2)-H(2) 110 H(28A)-C(28)-H(28B) 109.5
C(8)-C(3)-C(4) 120.9(4) C(27)-C(28)-H(28C) 109.5
C(8)-C(3)-C(2) 125.7(4) H(28A)-C(28)-H(28C) 109.5
C(4)-C(3)-C(2) 113.4(4) H(28B)-C(28)-H(28C) 109.5
C(5)-C(4)-C(3) 119.6(4) C(27)-C(29)-H(29A) 109.5
C(5)-C(4)-B(1) 131.1(4) C(27)-C(29)-H(29B) 109.5
C(3)-C(4)-B(1) 109.2(4) H(29A)-C(29)-H(29B) 109.5
C(6)-C(5)-C(4) 119.9(4) C(27)-C(29)-H(29C) 109.5
C(6)-C(5)-H(5) 120.1 H(29A)-C(29)-H(29C) 109.5
C(4)-C(5)-H(5) 120.1 H(29B)-C(29)-H(29C) 109.5
C(5)-C(6)-C(7) 119.8(5) C(31)-C(30)-C(35) 120.2(4)
C(5)-C(6)-H(6) 120.1 C(31)-C(30)-B(2) 120.4(4)
C(7)-C(6)-H(6) 120.1 C(35)-C(30)-B(2) 119.2(4)
C(6)-C(7)-C(8) 121.4(4) C(30)-C(31)-C(32) 118.4(4)
C(6)-C(7)-H(7) 119.3 C(30)-C(31)-C(36) 120.8(4)
C(8)-C(7)-H(7) 119.3 C(32)-C(31)-C(36) 120.8(4)
C(7)-C(8)-C(3) 118.4(4) C(33)-C(32)-C(31) 122.3(5)
C(7)-C(8)-H(8) 120.8 C(33)-C(32)-H(32) 118.8
C(3)-C(8)-H(8) 120.8 C(31)-C(32)-H(32) 118.8
C(10)-C(9)-C(14) 120.2(4) C(34)-C(33)-C(32) 117.9(4)
C(10)-C(9)-C(1) 114.1(4) C(34)-C(33)-C(39) 119.8(4)
C(14)-C(9)-C(1) 125.8(4) C(32)-C(33)-C(39) 122.2(4)
C(9)-C(10)-C(11) 119.7(4) C(33)-C(34)-C(35) 122.1(4)
C(9)-C(10)-B(2) 108.3(4) C(33)-C(34)-H(34) 118.9
C(11)-C(10)-B(2) 132.0(4) C(35)-C(34)-H(34) 118.9
C(12)-C(11)-C(10) 119.2(4) C(34)-C(35)-C(30) 118.9(4)
C(12)-C(11)-H(11) 120.4 C(34)-C(35)-C(42) 121.0(4)
C(10)-C(11)-H(11) 120.4 C(30)-C(35)-C(42) 120.1(4)
C(13)-C(12)-C(11) 120.3(5) C(31)-C(36)-C(38) 111.7(5)
C(13)-C(12)-H(12) 119.8 C(31)-C(36)-C(37) 113.8(5)
C(11)-C(12)-H(12) 119.8 C(38)-C(36)-C(37) 110.2(5)
C(14)-C(13)-C(12) 121.7(4) C(31)-C(36)-H(36) 106.9
C(14)-C(13)-H(13) 119.1 C(38)-C(36)-H(36) 106.9
C(12)-C(13)-H(13) 119.1 C(37)-C(36)-H(36) 106.9
C(13)-C(14)-C(9) 118.9(4) C(36)-C(37)-H(37A) 109.5
C(13)-C(14)-H(14) 120.5 C(36)-C(37)-H(37B) 109.5
194
C(9)-C(14)-H(14) 120.5 H(37A)-C(37)-H(37B) 109.5
C(16)-C(15)-C(20) 119.4(4) C(36)-C(37)-H(37C) 109.5
C(16)-C(15)-B(1) 121.8(4) H(37A)-C(37)-H(37C) 109.5
C(20)-C(15)-B(1) 118.7(4) H(37B)-C(37)-H(37C) 109.5
C(15)-C(16)-C(17) 119.5(4) C(36)-C(38)-H(38A) 109.5
C(15)-C(16)-C(21) 120.0(4) C(36)-C(38)-H(38B) 109.5
C(17)-C(16)-C(21) 120.5(4) H(38A)-C(38)-H(38B) 109.5
C(18)-C(17)-C(16) 121.8(4) C(36)-C(38)-H(38C) 109.5
C(18)-C(17)-H(17) 119.1 H(38A)-C(38)-H(38C) 109.5
C(16)-C(17)-H(17) 119.1 H(38B)-C(38)-H(38C) 109.5
C(17)-C(18)-C(19) 118.3(4) C(41)-C(39)-C(40) 111.5(5)
C(17)-C(18)-C(24) 122.3(4) C(41)-C(39)-C(33) 111.4(4)
C(19)-C(18)-C(24) 119.4(4) C(40)-C(39)-C(33) 112.5(4)
C(18)-C(19)-C(20) 121.2(4) C(41)-C(39)-H(39) 107
C(18)-C(19)-H(19) 119.4 C(40)-C(39)-H(39) 107
C(20)-C(19)-H(19) 119.4 C(33)-C(39)-H(39) 107
C(15)-C(20)-C(19) 119.7(4) C(39)-C(40)-H(40A) 109.5
C(15)-C(20)-C(27) 120.2(4) C(39)-C(40)-H(40B) 109.5
C(19)-C(20)-C(27) 120.1(4) H(40A)-C(40)-H(40B) 109.5
C(16)-C(21)-C(22) 113.9(4) C(39)-C(40)-H(40C) 109.5
C(16)-C(21)-C(23) 111.1(5) H(40A)-C(40)-H(40C) 109.5
C(22)-C(21)-C(23) 109.6(4) H(40B)-C(40)-H(40C) 109.5
C(16)-C(21)-H(21) 107.3 C(39)-C(41)-H(41A) 109.5
C(22)-C(21)-H(21) 107.3 C(39)-C(41)-H(41B) 109.5
C(23)-C(21)-H(21) 107.3 H(41A)-C(41)-H(41B) 109.5
C(21)-C(22)-H(22A) 109.5 C(39)-C(41)-H(41C) 109.5
C(21)-C(22)-H(22B) 109.5 H(41A)-C(41)-H(41C) 109.5
H(22A)-C(22)-H(22B) 109.5 H(41B)-C(41)-H(41C) 109.5
C(21)-C(22)-H(22C) 109.5 C(35)-C(42)-C(43) 113.3(4)
H(22A)-C(22)-H(22C) 109.5 C(35)-C(42)-C(44) 111.7(4)
H(22B)-C(22)-H(22C) 109.5 C(43)-C(42)-C(44) 111.1(4)
C(21)-C(23)-H(23A) 109.5 C(35)-C(42)-H(42) 106.8
C(21)-C(23)-H(23B) 109.5 C(43)-C(42)-H(42) 106.8
H(23A)-C(23)-H(23B) 109.5 C(44)-C(42)-H(42) 106.8
C(21)-C(23)-H(23C) 109.5 C(42)-C(43)-H(43A) 109.5
H(23A)-C(23)-H(23C) 109.5 C(42)-C(43)-H(43B) 109.5
H(23B)-C(23)-H(23C) 109.5 H(43A)-C(43)-H(43B) 109.5
C(26)-C(24)-C(18) 111.5(4) C(42)-C(43)-H(43C) 109.5
C(26)-C(24)-C(25) 110.7(4) H(43A)-C(43)-H(43C) 109.5
C(18)-C(24)-C(25) 113.5(4) H(43B)-C(43)-H(43C) 109.5
C(26)-C(24)-H(24) 106.9 C(42)-C(44)-H(44A) 109.5
C(18)-C(24)-H(24) 106.9 C(42)-C(44)-H(44B) 109.5
C(25)-C(24)-H(24) 106.9 H(44A)-C(44)-H(44B) 109.5
C(24)-C(25)-H(25A) 109.5 C(42)-C(44)-H(44C) 109.5
C(24)-C(25)-H(25B) 109.5 H(44A)-C(44)-H(44C) 109.5
H(25A)-C(25)-H(25B) 109.5 H(44B)-C(44)-H(44C) 109.5
C(24)-C(25)-H(25C) 109.5 C(4)-B(1)-C(15) 131.2(4)
H(25A)-C(25)-H(25C) 109.5 C(4)-B(1)-C(1) 105.4(4)
H(25B)-C(25)-H(25C) 109.5 C(15)-B(1)-C(1) 123.4(4)
C(24)-C(26)-H(26A) 109.5 C(10)-B(2)-C(30) 131.0(4)
C(24)-C(26)-H(26B) 109.5 C(10)-B(2)-C(2) 105.7(4)
H(26A)-C(26)-H(26B) 109.5 C(30)-B(2)-C(2) 123.3(4)
195
Empirical formula C122 H172 B4 K4 O10
Space group P-1
b = 15.3414(7) Å β = 78.224(3) º
c = 16.5198(9) Å γ = 64.155(3) º
Volume 3194.1(3) Å3
Z 1
F(000) 1080
Limiting indices -17 <= h <= 17 ; -18 <= k <= 18 ; -19 <= l <= 19
Completeness to theta max 96.9 %
Atom x y z U(eq)
B1 7724.4(1.5) 7755.6(1.3) 7176.8(1.2) 39.0(4)
B2 9047.5(1.4) 9837.9(1.3) 7390.1(1.1) 37.3(4)
C1 8381.1(1.4) 7327.2(1.2) 6278.5(1.1) 41.7(4)
C10 7077.4(1.6) 9095.8(1.4) 8823.6(1.2) 50.3(4)
C11 6851(2) 9645.8(1.8) 9541.0(1.3) 63.0(6)
C12 7325(2) 10270.7(1.8) 9583.5(1.3) 63.8(6)
C13 8020.7(1.7) 10316.9(1.4) 8905.7(1.2) 50.7(4)
C14 8282.3(1.3) 9765.3(1.2) 8145.8(1.0) 39.1(3)
C15 9267.8(1.3) 9230.3(1.2) 6577.2(1.0) 36.8(3)
C16 6977.2(1.4) 7335.0(1.2) 7706.2(1.1) 41.5(4)
C17 7416.4(1.6) 6411.5(1.3) 8022.3(1.2) 48.0(4)
C18 6758.1(1.8) 6026.9(1.5) 8457.8(1.4) 57.7(5)
C19 5668.6(1.9) 6517.8(1.7) 8597.9(1.6) 62.9(5)
C2 8493.3(1.7) 6561.1(1.4) 5768.8(1.2) 51.7(4)
C20 5232.9(1.7) 7427.2(1.7) 8284.4(1.5) 57.8(5)
C21 5865.1(1.5) 7836.5(1.3) 7850.5(1.2) 45.9(4)
C22 8612.5(1.7) 5846.6(1.4) 7917.8(1.5) 55.7(5)
C23 8947(2) 5845(2) 8734.4(1.9) 81.2(7)
C24 9041(2) 4808.8(1.8) 7533(2) 87.4(9)
196
C25 4983(2) 6057(2) 9068(2) 88.5(9)
C26 4641(5) 5589(5) 8500(4) 180(3)
C27 4106(4) 6711(4) 9722(3) 131.3(1.8)
C28 5355.6(1.5) 8826.7(1.4) 7505.7(1.4) 52.5(4)
C29 4964(3) 8742(2) 6741.8(1.9) 82.3(8)
C3 9241(2) 6263.8(1.4) 5023.0(1.3) 58.3(5)
C30 4472(2) 9584.8(1.9) 8155(2) 77.8(7)
C31 9667.7(1.3) 10487.6(1.2) 7383.2(1.0) 37.8(3)
C32 10728.8(1.4) 10068.3(1.3) 7472.5(1.1) 42.8(4)
C33 11324.6(1.4) 10593.4(1.4) 7331.5(1.2) 47.0(4)
C34 10886.1(1.4) 11555.6(1.3) 7127.4(1.2) 45.0(4)
C35 9823.9(1.4) 11987.3(1.2) 7086.9(1.1) 43.0(4)
C36 9216.5(1.3) 11467.5(1.2) 7211(1) 39.7(3)
C37 11225.7(1.6) 9028.6(1.5) 7728.3(1.5) 55.2(5)
C38 11913(3) 8318.1(1.9) 6998(2) 89.8(9)
C39 11813(3) 8922(2) 8425(2) 92(1)
C4 9888.0(1.8) 6720.3(1.4) 4788.5(1.1) 55.8(5)
C40 11545.0(1.6) 12121.6(1.5) 6953.4(1.6) 57.3(5)
C41 11921(3) 12241(3) 7732(2) 100.6(1.1)
C42 12448(2) 11668(2) 6197(2) 88.8(1.0)
C43 8061.3(1.4) 11971.1(1.4) 7141.7(1.3) 48.8(4)
C44 7964(2) 12194(2) 6248.3(1.7) 79.3(8)
C45 7416.9(1.8) 12880(2) 7716.6(1.8) 75.3(7)
C46 12386(4) 5107(4) 7435(4) 159(3)
C47 13007(4) 4305(3) 6776(4) 134.2(1.7)
C48 12278(5) 4427(4) 6272(4) 149(2)
C49 11533(5) 5435(4) 6369(3) 132.6(1.7)
C5 9781.9(1.6) 7506.6(1.3) 5270.0(1.1) 47.2(4)
C50 11092(6) 6616(4) 9750(4) 162(3)
C51 11077(6) 6974(6) 10523(4) 168(3)
C52 10469(7) 8023(5) 10507(3) 172(3)
C53 9764(6) 8108(4) 9934(3) 166(3)
C54 13737(3) 8483(3) 4928(2) 90.3(9)
C55 14574(4) 8217(4) 4166(5) 165(3)
C56 14301(6) 9089(4) 3702(4) 188(3)
C57 13453(3) 9824(4) 4180(4) 151(2)
C58 5104(6) 3751(5) 3927(7) 197(4)
C59 4094(5) 3914(4) 3882(5) 148(2)
C6 9019.9(1.3) 7818.4(1.1) 6006.5(1.0) 38.4(3)
C60 3509(5) 4920(5) 3840(5) 153(2)
C61 4236(7) 5352(5) 3969(7) 213(4)
C7 8803.1(1.2) 8579.0(1.1) 6643.7(9) 35.6(3)
C8 8052.1(1.2) 8535.2(1.1) 7359(1) 36.1(3)
C9 7787.7(1.3) 9134.7(1.2) 8105.8(1.0) 38.4(3)
K1 10024.0(4) 7424.2(3) 7854.8(4) 66.02(16)
K2 10901.9(3) 10321.7(3) 5457.9(2) 47.31(13)
O1 9867.6(1.1) 9299.6(1.0) 5883.7(8) 49.3(3)
O2 11515(2) 5765(2) 7176.1(1.9) 126.6(1.1)
O3 10397(3) 7310.1(1.9) 9343.7(1.6) 112.7(9)
O4 12998.8(1.6) 9421.2(1.8) 4836.0(1.7) 102.1(8)
O5 5219(5) 4597(5) 3864(6) 271(4)
197
B1 - C1 1.570(2) C43 - C45 1.514(3)
B1 - C16 1.587(2) C43 - H43A 1
B1 - C8 1.520(2) C44 - H44A 0.98
B2 - C14 1.521(3) C44 - H44B 0.98
B2 - C15 1.553(2) C44 - H44C 0.98
B2 - C31 1.598(2) C45 - H45A 0.98
C1 - C2 1.397(2) C45 - H45B 0.98
C1 - C6 1.423(2) C45 - H45C 0.98
C10 - C11 1.372(3) C46 - C47 1.490(7)
C10 - H10A 0.95 C46 - H46A 0.99
C11 - C12 1.407(3) C46 - H46B 0.99
C11 - H11A 0.95 C47 - C48 1.413(7)
C12 - C13 1.362(3) C47 - H47A 0.99
C12 - H12A 0.95 C47 - H47B 0.99
C13 - C14 1.422(2) C48 - C49 1.437(7)
C13 - H13A 0.95 C48 - H48A 0.99
C15 - K2 3.4486(16) C48 - H48B 0.99
C16 - C17 1.411(3) C49 - H49A 0.99
C16 - C21 1.406(3) C49 - H49B 0.99
C17 - C18 1.393(3) C5 - C6 1.392(2)
C17 - C22 1.521(3) C5 - H5A 0.95
C18 - C19 1.378(3) C5 - K2 3.3038(19)
C18 - H18A 0.95 C50 - C51 1.397(7)
C19 - C20 1.392(3) C50 - H50A 0.99
C19 - C25 1.527(3) C50 - H50B 0.99
C2 - C3 1.393(3) C51 - C52 1.462(9)
C2 - H2A 0.95 C51 - H51A 0.99
C20 - C21 1.391(3) C51 - H51B 0.99
C20 - H20A 0.95 C52 - C53 1.484(9)
C21 - C28 1.523(3) C52 - H52A 0.99
C22 - C23 1.521(4) C52 - H52B 0.99
C22 - C24 1.536(3) C53 - H53A 0.99
C22 - H22A 1 C53 - H53B 0.99
C23 - H23A 0.98 C54 - C55 1.476(6)
C23 - H23B 0.98 C54 - H54A 0.99
C23 - H23C 0.98 C54 - H54B 0.99
C24 - H24A 0.98 C55 - C56 1.462(8)
C24 - H24B 0.98 C55 - H55A 0.99
C24 - H24C 0.98 C55 - H55B 0.99
C25 - C26 1.473(6) C56 - C57 1.356(6)
C25 - C27 1.470(5) C56 - H56A 0.99
C25 - H25A 1 C56 - H56B 0.99
C26 - H26A 0.98 C57 - H57A 0.99
C26 - H26B 0.98 C57 - H57B 0.99
C26 - H26C 0.98 C58 - H58A 0.99
C27 - H27A 0.98 C58 - H58B 0.99
C27 - H27B 0.98 C59 - C58 1.376(8)
C27 - H27C 0.98 C59 - C60 1.407(8)
C28 - C29 1.512(3) C59 - H59A 0.99
C28 - C30 1.530(3) C59 - H59B 0.99
C28 - H28A 1 C6 - C7 1.478(2)
C29 - H29A 0.98 C60 - H60A 0.99
C29 - H29B 0.98 C60 - H60B 0.99
C29 - H29C 0.98 C61 - C60 1.508(9)
198
C3 - C4 1.380(3) C61 - H61A 0.99
C3 - H3A 0.95 C61 - H61B 0.99
C30 - H30A 0.98 C7 - C15 1.414(2)
C30 - H30B 0.98 C7 - C8 1.449(2)
C30 - H30C 0.98 C8 - C9 1.442(2)
C31 - C32 1.408(2) C9 - C10 1.415(3)
C31 - C36 1.401(2) C9 - C14 1.437(2)
C32 - C33 1.393(2) K1 - B1 3.5212(19)
C32 - C37 1.525(3) K1 - B2 3.4670(19)
C33 - C34 1.392(3) K1 - C14 3.3398(17)
C33 - H33A 1 K1 - C15 3.3606(17)
C34 - C35 1.387(3) K1 - C7 2.9550(16)
C34 - C40 1.523(2) K1 - C8 2.8697(16)
C35 - C36 1.400(2) K1 - C9 3.0858(17)
C35 - H35A 1 K1 - O2 2.597(2)
C36 - C43 1.520(2) K1 - O3 2.608(2)
C37 - C38 1.506(4) K2 - C15 3.4487(16)
C37 - C39 1.525(4) K2 - C31 3.2662(16)
C37 - H37A 1 K2 - C32 3.3109(18)
C38 - H38A 0.98 K2 - C33 3.3435(19)
C38 - H38B 0.98 K2 - C34 3.3794(18)
C38 - H38C 0.98 K2 - C35 3.3770(18)
C39 - H39A 0.98 K2 - C36 3.3232(16)
C39 - H39B 0.98 K2 - C5 3.3038(19)
C39 - H39C 0.98 K2 - K2 3.7231(8)
C4 - C5 1.398(3) K2 - O1 2.6143(14)
C4 - H4A 0.95 K2 - O4 2.684(2)
C40 - C41 1.536(4) O1 - C15 1.317(2)
C40 - C42 1.525(4) O1 - K2 2.6143(14)
C40 - H40A 1 O2 - C46 1.363(5)
C41 - H41A 0.98 O2 - C49 1.431(5)
C41 - H41B 0.98 O3 - C50 1.373(5)
C41 - H41C 0.98 O3 - C53 1.418(6)
C42 - H42A 0.98 O4 - C54 1.393(4)
C42 - H42B 0.98 O4 - C57 1.415(5)
C42 - H42C 0.98 O5 - C58 1.377(8)
C43 - C44 1.526(3) O5 - C61 1.359(9)

B1 - C8 - K1 102.27(10) C48 - C49 - H49B 110.7
B2 - C14 - K1 81.80(9) C49 - C48 - H48A 110.3
B2 - C15 - K1 80.71(9) C49 - C48 - H48B 110.3
B2 - C15 - K2 136.77(11) C49 - O2 - K1 120.1(2)
B2 - C31 - K2 105.07(9) C5 - C4 - H4A 119.4
B2 - K1 - B1 78.49(4) C5 - C6 - C1 120.59(15)
C1 - B1 - C16 122.45(14) C5 - C6 - C7 129.19(16)
C1 - B1 - K1 91.65(10) C5 - K2 - C15 56.32(4)
C1 - C2 - H2A 119.7 C5 - K2 - C32 120.36(4)
C1 - C6 - C7 109.97(14) C5 - K2 - C33 104.25(5)
C10 - C11 - C12 120.47(19) C5 - K2 - C34 80.63(5)
C10 - C11 - H11A 119.8 C5 - K2 - C35 71.92(4)
C10 - C9 - C14 118.16(15) C5 - K2 - C36 86.31(4)
C10 - C9 - C8 121.81(15) C5 - K2 - K2 96.71(4)
199
C10 - C9 - K1 113.53(12) C50 - C51 - C52 103.4(5)
C11 - C10 - C9 121.73(17) C50 - C51 - H51A 111.1
C11 - C10 - H10A 119.1 C50 - C51 - H51B 111.1
C11 - C12 - H12A 120.4 C50 - O3 - C53 105.9(4)
C12 - C11 - H11A 119.8 C50 - O3 - K1 135.3(3)
C12 - C13 - C14 122.69(17) C51 - C50 - H50A 109.1
C12 - C13 - H13A 118.7 C51 - C50 - H50B 109.1
C13 - C12 - C11 119.20(17) C51 - C52 - C53 103.0(4)
C13 - C12 - H12A 120.4 C51 - C52 - H52A 111.2
C13 - C14 - B2 122.01(15) C51 - C52 - H52B 111.2
C13 - C14 - C9 117.74(16) C52 - C51 - H51A 111.1
C13 - C14 - K1 122.21(13) C52 - C51 - H51B 111.1
C14 - B2 - C15 118.74(14) C52 - C53 - H53A 111.1
C14 - B2 - C31 123.93(14) C52 - C53 - H53B 111.1
C14 - B2 - K1 72.45(9) C53 - C52 - H52A 111.2
C14 - C13 - H13A 118.7 C53 - C52 - H52B 111.2
C14 - C9 - C8 119.98(15) C53 - O3 - K1 118.8(3)
C14 - C9 - K1 87.20(10) C54 - C55 - H55A 110.5
C14 - K1 - B1 70.39(4) C54 - C55 - H55B 110.5
C14 - K1 - B2 25.74(4) C54 - O4 - C57 109.4(2)
C14 - K1 - C15 46.51(4) C54 - O4 - K2 129.9(2)
C15 - B2 - C31 117.31(14) C55 - C54 - H54A 110.7
C15 - B2 - K1 73.06(9) C55 - C54 - H54B 110.7
C15 - C7 - C6 125.80(14) C55 - C56 - H56A 110.1
C15 - C7 - C8 125.33(14) C55 - C56 - H56B 110.1
C15 - C7 - K1 93.86(10) C56 - C55 - C54 106.0(4)
C15 - K1 - B1 66.73(4) C56 - C55 - H55A 110.5
C15 - K1 - B2 26.24(4) C56 - C55 - H55B 110.5
C15 - K2 - K2 60.71(3) C56 - C57 - H57A 110
C15 - O1 - K2 118.87(10) C56 - C57 - H57B 110
C16 - B1 - K1 117.79(11) C56 - C57 - O4 108.4(4)
C16 - C17 - C22 120.06(17) C57 - C56 - C55 107.9(4)
C16 - C21 - C28 119.20(16) C57 - C56 - H56A 110.1
C17 - C16 - B1 120.45(16) C57 - C56 - H56B 110.1
C17 - C18 - H18A 118.8 C57 - O4 - K2 119.27(19)
C17 - C22 - C24 112.6(2) C58 - C59 - C60 107.1(5)
C17 - C22 - H22A 107.2 C58 - C59 - H59A 110.3
C18 - C17 - C16 120.32(18) C58 - C59 - H59B 110.3
C18 - C17 - C22 119.57(18) C59 - C58 - H58A 109.4
C18 - C19 - C20 117.5(2) C59 - C58 - H58B 109.4
C18 - C19 - C25 120.3(2) C59 - C58 - O5 111.1(5)
C19 - C18 - C17 122.3(2) C59 - C60 - C61 105.0(5)
C19 - C18 - H18A 118.8 C59 - C60 - H60A 110.7
C19 - C20 - H20A 119.1 C59 - C60 - H60B 110.7
C19 - C25 - H25A 105.7 C6 - C1 - B1 108.10(14)
C2 - C1 - B1 133.11(17) C6 - C5 - C4 118.93(18)
C2 - C1 - C6 118.61(16) C6 - C5 - H5A 120.5
C2 - C3 - H3A 120.1 C6 - C5 - K2 95.83(11)
C20 - C19 - C25 122.2(2) C6 - C7 - K1 101.72(10)
C20 - C21 - C16 120.73(18) C60 - C59 - H59A 110.3
C20 - C21 - C28 120.05(17) C60 - C59 - H59B 110.3
C21 - C16 - B1 122.16(16) C60 - C61 - H61A 110.6
C21 - C16 - C17 117.34(16) C60 - C61 - H61B 110.6
C21 - C20 - C19 121.8(2) C61 - C60 - H60A 110.7
200
C21 - C20 - H20A 119.1 C61 - C60 - H60B 110.7
C21 - C28 - C30 112.4(2) C61 - O5 - C58 108.0(6)
C21 - C28 - H28A 107.4 C7 - C15 - B2 115.08(14)
C22 - C23 - H23A 109.5 C7 - C15 - K1 61.32(8)
C22 - C23 - H23B 109.5 C7 - C15 - K2 95.16(9)
C22 - C23 - H23C 109.5 C7 - C8 - B1 109.07(14)
C22 - C24 - H24A 109.5 C7 - C8 - K1 78.89(9)
C22 - C24 - H24B 109.5 C7 - K1 - B1 42.74(4)
C22 - C24 - H24C 109.5 C7 - K1 - B2 45.04(4)
C23 - C22 - C17 111.1(2) C7 - K1 - C14 54.20(4)
C23 - C22 - C24 111.2(2) C7 - K1 - C15 24.82(4)
C23 - C22 - H22A 107.2 C7 - K1 - C9 48.95(4)
C24 - C22 - H22A 107.2 C8 - B1 - C1 103.92(14)
C25 - C26 - H26A 109.5 C8 - B1 - C16 133.53(15)
C25 - C26 - H26B 109.5 C8 - B1 - K1 52.78(8)
C25 - C26 - H26C 109.5 C8 - C7 - C6 108.85(14)
C25 - C27 - H27A 109.5 C8 - C7 - K1 72.35(9)
C25 - C27 - H27B 109.5 C8 - C9 - K1 67.77(9)
C25 - C27 - H27C 109.5 C8 - K1 - B1 24.94(4)
C26 - C25 - C19 111.7(3) C8 - K1 - B2 53.99(4)
C26 - C25 - H25A 105.7 C8 - K1 - C14 46.59(4)
C27 - C25 - C19 113.9(3) C8 - K1 - C15 47.38(4)
C27 - C25 - C26 113.2(4) C8 - K1 - C7 28.76(4)
C27 - C25 - H25A 105.7 C8 - K1 - C9 27.73(4)
C28 - C29 - H29A 109.5 C9 - C10 - H10A 119.1
C28 - C29 - H29B 109.5 C9 - C14 - B2 120.24(14)
C28 - C29 - H29C 109.5 C9 - C14 - K1 67.35(9)
C28 - C30 - H30A 109.5 C9 - C8 - B1 130.65(15)
C28 - C30 - H30B 109.5 C9 - C8 - C7 120.14(14)
C28 - C30 - H30C 109.5 C9 - C8 - K1 84.50(10)
C29 - C28 - C21 110.41(18) C9 - K1 - B1 47.52(4)
C29 - C28 - C30 111.5(2) C9 - K1 - B2 45.63(4)
C29 - C28 - H28A 107.4 C9 - K1 - C14 25.45(4)
C3 - C2 - C1 120.62(19) C9 - K1 - C15 55.15(4)
C3 - C2 - H2A 119.7 H23A - C23 - H23B 109.5
C3 - C4 - C5 121.27(18) H23A - C23 - H23C 109.5
C3 - C4 - H4A 119.4 H23B - C23 - H23C 109.5
C30 - C28 - H28A 107.4 H24A - C24 - H24B 109.5
C31 - B2 - K1 124.32(10) H24A - C24 - H24C 109.5
C31 - C32 - C37 119.37(15) H24B - C24 - H24C 109.5
C31 - C32 - K2 75.86(10) H26A - C26 - H26B 109.5
C31 - C36 - C43 119.93(15) H26A - C26 - H26C 109.5
C31 - C36 - K2 75.46(9) H26B - C26 - H26C 109.5
C31 - K2 - C15 147.99(4) H27A - C27 - H27B 109.5
C31 - K2 - C32 24.72(4) H27A - C27 - H27C 109.5
C31 - K2 - C33 43.22(4) H27B - C27 - H27C 109.5
C31 - K2 - C34 50.58(4) H29A - C29 - H29B 109.5
C31 - K2 - C35 42.95(4) H29A - C29 - H29C 109.5
C31 - K2 - C36 24.53(4) H29B - C29 - H29C 109.5
C31 - K2 - C5 110.81(4) H30A - C30 - H30B 109.5
C31 - K2 - K2 95.86(3) H30A - C30 - H30C 109.5
C32 - C31 - B2 120.72(15) H30B - C30 - H30C 109.5
C32 - C31 - K2 79.42(10) H38A - C38 - H38B 109.5
C32 - C33 - H33A 119.2 H38A - C38 - H38C 109.5
201
C32 - C33 - K2 76.61(11) H38B - C38 - H38C 109.5
C32 - C37 - H37A 106.6 H39A - C39 - H39B 109.5
C32 - K2 - C15 172.58(4) H39A - C39 - H39C 109.5
C32 - K2 - C33 24.17(4) H39B - C39 - H39C 109.5
C32 - K2 - C34 42.58(4) H41A - C41 - H41B 109.5
C32 - K2 - C35 48.87(4) H41A - C41 - H41C 109.5
C32 - K2 - C36 42.45(4) H41B - C41 - H41C 109.5
C32 - K2 - K2 115.05(3) H42A - C42 - H42B 109.5
C33 - C32 - C31 120.74(16) H42A - C42 - H42C 109.5
C33 - C32 - C37 119.89(16) H42B - C42 - H42C 109.5
C33 - C32 - K2 79.23(11) H44A - C44 - H44B 109.5
C33 - C34 - C40 121.46(17) H44A - C44 - H44C 109.5
C33 - C34 - K2 76.61(11) H44B - C44 - H44C 109.5
C33 - K2 - C15 157.84(4) H45A - C45 - H45B 109.5
C33 - K2 - C34 23.89(5) H45A - C45 - H45C 109.5
C33 - K2 - C35 41.46(4) H45B - C45 - H45C 109.5
C33 - K2 - K2 138.46(4) H46A - C46 - H46B 108.4
C34 - C33 - C32 121.50(16) H47A - C47 - H47B 109.1
C34 - C33 - H33A 119.2 H48A - C48 - H48B 108.6
C34 - C33 - K2 79.50(11) H49A - C49 - H49B 108.8
C34 - C35 - C36 121.57(16) H50A - C50 - H50B 107.9
C34 - C35 - H35A 119.2 H51A - C51 - H51B 109
C34 - C35 - K2 78.25(10) H52A - C52 - H52B 109.1
C34 - C40 - C41 110.6(2) H53A - C53 - H53B 109
C34 - C40 - C42 111.22(19) H54A - C54 - H54B 108.8
C34 - C40 - H40A 107.1 H55A - C55 - H55B 108.7
C34 - K2 - C15 136.26(4) H56A - C56 - H56B 108.4
C34 - K2 - K2 140.53(3) H57A - C57 - H57B 108.4
C35 - C34 - C33 117.81(16) H58A - C58 - H58B 108
C35 - C34 - C40 120.73(17) H59A - C59 - H59B 108.5
C35 - C34 - K2 78.06(10) H60A - C60 - H60B 108.8
C35 - C36 - C31 120.69(15) H61A - C61 - H61B 108.7
C35 - C36 - C43 119.37(16) K1 - C15 - K2 142.47(5)
C35 - C36 - K2 80.11(10) K2 - C33 - H33A 119.2
C35 - K2 - C15 126.40(4) K2 - C35 - H35A 119.2
C35 - K2 - C34 23.69(4) K2 - C5 - H5A 52.5
C35 - K2 - K2 118.18(3) K2 - O1 - K2 91.41(4)
C36 - C31 - B2 121.50(15) O1 - C15 - B2 122.29(14)
C36 - C31 - C32 117.51(15) O1 - C15 - C7 122.60(14)
C36 - C31 - K2 80.01(10) O1 - C15 - K1 125.28(11)
C36 - C35 - H35A 119.2 O1 - C15 - K2 41.59(8)
C36 - C35 - K2 75.79(9) O1 - K2 - C15 19.54(4)
C36 - C43 - C44 111.23(17) O1 - K2 - C31 129.22(4)
C36 - C43 - H43A 107.2 O1 - K2 - C32 153.74(4)
C36 - K2 - C15 130.53(4) O1 - K2 - C33 161.32(5)
C36 - K2 - C33 49.10(4) O1 - K2 - C34 138.22(5)
C36 - K2 - C34 42.54(4) O1 - K2 - C35 120.02(5)
C36 - K2 - C35 24.10(4) O1 - K2 - C36 116.01(4)
C36 - K2 - K2 98.11(3) O1 - K2 - C5 60.00(4)
C37 - C32 - K2 115.97(12) O1 - K2 - K2 44.00(3)
C37 - C38 - H38A 109.5 O1 - K2 - O1 88.59(4)
C37 - C38 - H38B 109.5 O1 - K2 - O4 102.15(7)
C37 - C38 - H38C 109.5 O2 - C46 - C47 108.5(4)
C37 - C39 - H39A 109.5 O2 - C46 - H46A 110
202
C37 - C39 - H39B 109.5 O2 - C46 - H46B 110
C37 - C39 - H39C 109.5 O2 - C49 - C48 105.2(4)
C38 - C37 - C32 111.9(2) O2 - C49 - H49A 110.7
C38 - C37 - C39 111.9(2) O2 - C49 - H49B 110.7
C38 - C37 - H37A 106.6 O2 - K1 - B1 106.69(8)
C39 - C37 - C32 112.71(19) O2 - K1 - B2 137.41(9)
C39 - C37 - H37A 106.6 O2 - K1 - C14 162.41(8)
C4 - C3 - C2 119.87(17) O2 - K1 - C15 116.01(8)
C4 - C3 - H3A 120.1 O2 - K1 - C7 111.40(7)
C4 - C5 - H5A 120.5 O2 - K1 - C8 126.62(7)
C4 - C5 - K2 121.11(13) O2 - K1 - C9 153.86(8)
C40 - C34 - K2 115.12(13) O2 - K1 - O3 99.73(9)
C40 - C41 - H41A 109.5 O3 - C50 - C51 112.3(5)
C40 - C41 - H41B 109.5 O3 - C50 - H50A 109.1
C40 - C41 - H41C 109.5 O3 - C50 - H50B 109.1
C40 - C42 - H42A 109.5 O3 - C53 - C52 103.5(5)
C40 - C42 - H42B 109.5 O3 - C53 - H53A 111.1
C40 - C42 - H42C 109.5 O3 - C53 - H53B 111.1
C41 - C40 - H40A 107.1 O3 - K1 - B1 130.61(9)
C42 - C40 - C41 113.3(2) O3 - K1 - B2 108.32(7)
C42 - C40 - H40A 107.1 O3 - K1 - C14 94.68(7)
C43 - C36 - K2 114.33(11) O3 - K1 - C15 134.12(7)
C43 - C44 - H44A 109.5 O3 - K1 - C7 148.74(7)
C43 - C44 - H44B 109.5 O3 - K1 - C8 127.94(8)
C43 - C44 - H44C 109.5 O3 - K1 - C9 102.08(8)
C43 - C45 - H45A 109.5 O4 - C54 - C55 105.1(3)
C43 - C45 - H45B 109.5 O4 - C54 - H54A 110.7
C43 - C45 - H45C 109.5 O4 - C54 - H54B 110.7
C44 - C43 - H43A 107.2 O4 - C57 - H57A 110
C45 - C43 - C36 112.95(17) O4 - C57 - H57B 110
C45 - C43 - C44 110.7(2) O4 - K2 - C15 84.30(7)
C45 - C43 - H43A 107.2 O4 - K2 - C31 127.61(7)
C46 - C47 - H47A 111.1 O4 - K2 - C32 103.09(7)
C46 - C47 - H47B 111.1 O4 - K2 - C33 90.72(7)
C46 - O2 - C49 108.6(3) O4 - K2 - C34 99.44(8)
C46 - O2 - K1 131.3(3) O4 - K2 - C35 122.47(8)
C47 - C46 - H46A 110 O4 - K2 - C36 139.59(7)
C47 - C46 - H46B 110 O4 - K2 - C5 102.64(6)
C47 - C48 - C49 107.0(5) O4 - K2 - K2 119.33(7)
C47 - C48 - H48A 110.3 O5 - C58 - H58A 109.4
C47 - C48 - H48B 110.3 O5 - C58 - H58B 109.4
C48 - C47 - C46 103.3(4) O5 - C61 - C60 105.8(5)
C48 - C47 - H47A 111.1 O5 - C61 - H61A 110.6
C48 - C47 - H47B 111.1 O5 - C61 - H61B 110.6
C48 - C49 - H49A 110.7
203
APPENDIX B: THEORETICAL CALCULATIONS
Table B-1 Optimized x,y,z coordinates for 2-4Tip calculated on Gaussian 09 at the B3LYP//6-31g(d) level
C 0.217594 1.961584 -0.335584
C -1.034959 2.631989 -0.371370
C -1.095545 4.013671 -0.562727
C 0.112357 4.701506 -0.718128
C 1.345770 4.023065 -0.687560
C 1.429402 2.639817 -0.497743
C -0.318073 0.594894 -0.112799
C -0.240207 -1.961833 0.325532
C 1.013039 -2.630972 0.362347
C 1.074785 -4.012545 0.554135
C -0.132560 -4.701517 0.708877
C -1.366606 -4.024263 0.677737
C -1.451393 -2.641109 0.487800
C 0.294172 -0.594730 0.102687
B -1.776243 1.251399 -0.189607
B 1.752935 -1.249245 0.183380
C 3.234392 -0.731873 0.138877
C 3.969322 -0.743466 -1.082879
C 5.271200 -0.228506 -1.118717
C 5.906428 0.292049 0.009024
C 5.190110 0.272613 1.203878
C 3.882152 -0.221845 1.300848
C -5.940316 -0.258117 0.011138
C -5.292184 0.254526 1.131843
C -3.984630 0.759166 1.089857
C -3.259636 0.740505 -0.134933
C -3.920611 0.233568 -1.293746
C -5.231444 -0.247130 -1.191285
C 3.460927 -1.338634 -2.402305
C 7.322364 0.848301 -0.048053
C 3.263810 -0.181664 2.704917
C -7.362825 -0.792712 0.103134
C -3.467361 1.350421 2.407389
C -3.306783 0.186565 -2.699688
C 2.851902 -1.564419 3.242142
C 2.124501 0.844775 2.847392
C 2.091653 -0.825830 -2.878772
C 3.505413 -2.880538 -2.390607
C 7.429161 2.055258 -0.999035
C 8.350828 -0.237822 -0.416952
C -2.093320 0.840716 2.872803
C -3.515822 2.892349 2.400161
C -2.889643 1.565956 -3.241595
C -2.172784 -0.845671 -2.842436
C -8.342205 0.033202 -0.752417
C -7.441136 -2.288157 -0.258147
H -2.041219 4.549991 -0.595999
H 0.107410 5.777915 -0.869654
204
H 2.260433 4.597365 -0.816073
H 2.388940 2.131613 -0.476121
H 2.020922 -4.548001 0.588096
H -0.126660 -5.777915 0.860442
H -2.280783 -4.599429 0.805817
H -2.411344 -2.133684 0.465956
H 5.803424 -0.244600 -2.067781
H 5.666808 0.658414 2.103590
H -5.824645 0.270955 2.081585
H -5.711017 -0.625250 -2.091858
H 4.183372 -1.016408 -3.163528
H 7.568715 1.203522 0.962151
H 4.069105 0.167291 3.364346
H -7.676703 -0.691158 1.151240
H -4.183705 1.024116 3.172635
H -4.115505 -0.160174 -3.356120
H 1.996417 -1.985274 2.705522
H 3.678725 -2.279300 3.163274
H 2.568102 -1.487089 4.298842
H 1.247611 0.569520 2.254556
H 1.808885 0.914244 3.895747
H 2.448953 1.839656 2.523893
H 1.263916 -1.219344 -2.281426
H 2.037461 0.267786 -2.847756
H 1.916511 -1.146790 -3.912764
H 2.793036 -3.297940 -1.672191
H 3.250748 -3.277483 -3.381237
H 4.505271 -3.241787 -2.125737
H 7.209411 1.767882 -2.034111
H 6.725614 2.845896 -0.715840
H 8.441835 2.475796 -0.978641
H 8.169440 -0.632311 -1.423825
H 9.368684 0.170098 -0.397303
H 8.305888 -1.078938 0.283422
H -1.271127 1.241751 2.272933
H -1.913510 1.156734 3.907514
H -2.034162 -0.252422 2.835411
H -2.809647 3.312938 1.677403
H -4.518396 3.251948 2.143475
H -3.254896 3.287480 3.389891
H -2.030667 1.984065 -2.708390
H -2.609044 1.484587 -4.298842
H -3.712788 2.285032 -3.162321
H -1.293674 -0.574331 -2.251003
H -2.501844 -1.838554 -2.517466
H -1.858765 -0.917894 -3.891083
H -8.092866 -0.033017 -1.818085
H -9.368683 -0.332205 -0.627230
H -8.319085 1.091327 -0.469744
H -7.152220 -2.461455 -1.301541
H -6.775414 -2.884066 0.375864
H -8.463129 -2.664356 -0.129009
205
C -0.319793 -1.627881 0.816735

C 1.087446 -1.847299 0.882123
C 1.568160 -2.998215 1.491463
C 0.669541 -3.942476 2.029945
C -0.699657 -3.714565 1.961731
C -1.209017 -2.547661 1.355430
C -0.598484 -0.329088 0.158912
C 0.286593 1.627503 -0.815364
C -1.120661 1.846289 -0.882220
C -1.601220 2.997274 -1.491526
C -0.702401 3.942388 -2.028198
C 0.666836 3.715225 -1.958314
C 1.176048 2.548141 -1.352224
C 0.565122 0.328553 -0.157878
B 1.804935 -0.572025 0.267589
B -1.838248 0.570647 -0.268394
C -3.382668 0.291316 -0.155282
C -4.072985 -0.466563 -1.147437
C -5.453113 -0.671755 -1.031961
C -6.204134 -0.178471 0.035276
C -5.519557 0.549487 1.004779
C -4.142465 0.802285 0.934467
C 6.171108 0.173496 -0.041233
C 5.422372 0.662146 1.026319
C 4.040175 0.459742 1.144697
C 3.349334 -0.293312 0.152723
C 4.108667 -0.801963 -0.941556
C 5.484046 -0.551125 -1.015410
C -3.421929 -1.146675 -2.360853
C -7.703445 -0.420636 0.143686
C -3.585160 1.664700 2.075566
C 7.669369 0.428025 -0.132120
C 3.394310 1.139432 2.360790

C 3.546052 -1.661749 -2.082378
C -3.624901 3.167181 1.725296
C -2.201810 1.264816 2.606412
C -2.920069 -2.563256 -2.011744
C -2.331151 -0.349542 -3.088547
C -8.037677 -1.920550 0.251688
C -8.474326 0.233729 -1.018572
C 2.899224 2.559359 2.015181
C 2.300169 0.346400 3.087814
C 3.579463 -3.164452 -1.732544
C 2.163838 -1.255780 -2.611648
C 8.478575 -0.882384 -0.103050
C 8.033013 1.273840 -1.367203
H 2.639699 -3.173356 1.563205
H 1.048009 -4.844937 2.502485
H -1.390209 -4.441061 2.382840
206
H -2.281039 -2.374858 1.315991
H -2.672755 3.171850 -1.564593
H -1.080744 4.844937 -2.500674
H 1.357523 4.442405 -2.378018
H 2.248106 2.375819 -1.311626
H -5.952075 -1.247373 -1.809417
H -6.076530 0.945097 1.853154
H 5.930565 1.232693 1.802553
H 6.031832 -0.946335 -1.869061
H -4.234495 -1.277268 -3.088120
H -8.040631 0.059043 1.072966
H -4.283000 1.522925 2.911727
H 7.951157 1.008104 0.757583
H 4.208539 1.264342 3.087211
H 4.243329 -1.522811 -2.919461
H -2.923386 3.405948 0.919864
H -4.627589 3.469175 1.403369
H -3.350975 3.771867 2.598848

H -1.397162 1.515356 1.905613
H -1.985903 1.814395 3.530799
H -2.141957 0.194147 2.827435
H -2.089996 -2.531862 -1.298983
H -3.720217 -3.165556 -1.567399
H -2.567964 -3.078339 -2.914272
H -1.402852 -0.283599 -2.509962
H -2.075109 -0.852814 -4.028855
H -2.654479 0.668953 -3.324390
H -7.737378 -2.461099 -0.653820
H -7.521694 -2.380985 1.101357
H -9.116083 -2.068596 0.385442
H -8.269881 1.308552 -1.073800
H -8.192915 -0.209127 -1.981380
H -9.555164 0.097181 -0.892351
H 2.068089 2.533308 1.303357
H 2.550848 3.074416 2.919161

H 3.701792 3.158566 1.571032
H 1.371385 0.285455 2.509418
H 2.618930 -0.673840 3.322242
H 2.046779 0.849648 4.028855
H 2.878643 -3.400183 -0.925635
H 3.300678 -3.767647 -2.605596
H 4.581439 -3.471146 -1.412863
H 1.358631 -1.504686 -1.910929
H 2.107635 -0.184510 -2.830658
H 1.945478 -1.802931 -3.536898
H 8.257506 -1.505826 -0.977491
H 9.555165 -0.673194 -0.107284
H 8.248337 -1.470076 0.792341
H 9.107759 1.491582 -1.384842
H 7.784294 0.747853 -2.296640
H 7.491290 2.226045 -1.368053
207
B -1.748856 1.215171 0.112532

C -0.331427 0.602230 0.073202
C 0.203182 1.979008 0.284465
C 1.399460 2.671985 0.419843
H 2.367694 2.178022 0.379032
C 1.306220 4.071330 0.616539
H 2.221437 4.652529 0.728199
C 0.077777 4.725289 0.671204
H 0.053388 5.803876 0.824270
C -1.135854 4.006886 0.530302
H -2.088848 4.534713 0.575292
C -1.061329 2.636344 0.337682
C -3.242828 0.719241 -0.012579
C -3.968229 0.305228 1.128470
C -5.292815 -0.124041 1.001877
H -5.833102 -0.441891 1.893790
C -5.940214 -0.158747 -0.236959
C -5.219266 0.256517 -1.357985
H -5.710721 0.233008 -2.331566
C -3.893095 0.695112 -1.265528
C -3.315104 0.338240 2.504267
H -2.275253 0.661939 2.356879
C -3.264824 -1.047531 3.161036
H -4.272652 -1.437300 3.357077
H -2.734368 -0.999038 4.121290
H -2.742659 -1.766706 2.520968
C -3.986989 1.364178 3.428030
H -3.987133 2.361115 2.972996
H -3.456091 1.427598 4.387197
H -5.029330 1.090024 3.639599
C -7.378036 -0.632335 -0.372509
H -7.639919 -0.557976 -1.438481
C -8.356439 0.262604 0.402122
H -9.394409 -0.057813 0.238609
H -8.266068 1.309046 0.088632
H -8.160520 0.221867 1.480780
C -7.542315 -2.102710 0.038238
H -7.306736 -2.245216 1.100066
H -6.872219 -2.750003 -0.538696
H -8.574336 -2.442286 -0.124416
C -3.157048 1.140699 -2.522289
H -2.160735 1.480481 -2.206448
C -2.945886 -0.019136 -3.505228
H -2.398184 -0.840178 -3.030544
H -2.369727 0.314971 -4.378455
H -3.904238 -0.415063 -3.867421
C -3.847423 2.327533 -3.208364
H -4.839530 2.051784 -3.590039
208
H -3.250149 2.680304 -4.059501
H -3.975718 3.164685 -2.512730
B 1.748752 -1.215196 -0.112324
C 0.331327 -0.602251 -0.072912
C -0.203298 -1.979026 -0.284163
C -1.399586 -2.672000 -0.419467
H -2.367817 -2.178041 -0.378565
C -1.306359 -4.071340 -0.616215
H -2.221585 -4.652535 -0.727822
C -0.077921 -4.725294 -0.671001
H -0.053542 -5.803876 -0.824107
C 1.135720 -4.006894 -0.530169
H 2.088712 -4.534719 -0.575251
C 1.061208 -2.636359 -0.337490
C 3.242756 -0.719327 0.012651
C 3.968087 -0.305419 -1.128481
C 5.292737 0.123698 -1.002033
H 5.832964 0.441478 -1.894007
C 5.940273 0.158336 0.236733
C 5.219391 -0.256812 1.357843
H 5.710958 -0.233358 2.331370
C 3.893149 -0.695226 1.265535
C 3.314808 -0.338351 -2.504205
H 2.274956 -0.662003 -2.356714
C 3.264524 1.047455 -3.160903
H 4.272351 1.437183 -3.357027
H 2.733965 0.999036 -4.121106
H 2.742460 1.766625 -2.520746
C 3.986533 -1.364279 -3.428092
H 3.986687 -2.361236 -2.973102
H 3.455513 -1.427634 -4.387197
H 5.028862 -1.090164 -3.639781
C 7.378171 0.631745 0.372122
H 7.640162 0.557360 1.438065
C 8.356379 -0.263320 -0.402610
H 9.394408 0.056959 -0.239200
H 8.265902 -1.309752 -0.089114
H 8.160357 -0.222554 -1.481249
C 7.542585 2.102096 -0.038653
H 7.306906 2.244623 -1.100455
H 6.872633 2.749477 0.538352
H 8.574666 2.441548 0.123883
C 3.157214 -1.140785 2.522372
H 2.160538 -1.479699 2.206743
C 2.947253 0.018729 3.505941
H 2.400084 0.840448 3.031812
H 2.371048 -0.315357 4.379146
H 3.906004 0.413706 3.868112
C 3.847008 -2.328436 3.207621
H 4.839528 -2.053586 3.588879
H 3.249898 -2.681102 4.058918
H 3.974303 -3.165395 2.511572
209
C -0.609339 -0.261099 0.252324

C -0.329296 -1.354395 1.186597
C 1.085401 -1.556306 1.300017
C 1.560830 -2.557368 2.143926
H 2.634733 -2.723235 2.241400
C 0.668417 -3.361628 2.874693
H 1.047577 -4.143529 3.531556
C -0.707039 -3.155480 2.756154
H -1.397954 -3.778842 3.323156
C -1.212608 -2.152371 1.913726
H -2.287659 -1.999899 1.829688
C -3.351006 0.328161 -0.135220
C -4.102614 -0.572777 -0.925678
C -5.478725 -0.713731 -0.720561
H -6.037310 -1.413439 -1.342932
C -6.155799 0.016609 0.260662
C -5.409558 0.906090 1.035393
H -5.922499 1.483033 1.806268
C -4.031634 1.073685 0.852490
C -3.419232 -1.391389 -2.014441
H -2.347315 -1.154844 -1.969005
C -3.912461 -1.003164 -3.415472
H -4.981425 -1.223135 -3.539215
H -3.364154 -1.559770 -4.187159
H -3.764881 0.066740 -3.599841
C -3.555835 -2.902061 -1.780605
H -2.995717 -3.461713 -2.541386
H -4.604125 -3.225283 -1.834042
H -3.163929 -3.183679 -0.797285
C -7.650689 -0.140104 0.484364
H -7.921320 0.526362 1.316911
C -8.027213 -1.569213 0.901220
H -9.101328 -1.644362 1.119302
H -7.472355 -1.877609 1.794669
H -7.797201 -2.287677 0.104714
C -8.465534 0.303072 -0.739631
H -9.543684 0.240276 -0.537858
H -8.249986 -0.331880 -1.607976
H -8.226941 1.336035 -1.017954
C -3.271191 2.054861 1.735795
H -2.227702 2.054529 1.392285
C -3.262225 1.611820 3.205672
H -4.278079 1.592463 3.623068
H -2.662333 2.301447 3.814448
H -2.834139 0.609025 3.309708
C -3.794841 3.490676 1.596238
H -3.182140 4.183689 2.187875
H -4.831330 3.578693 1.948638
H -3.764995 3.819621 0.551376
B -1.790021 0.499899 -0.354971
210
C 0.609376 0.261054 -0.252403
C 0.329337 1.354411 -1.186606
C -1.085359 1.556337 -1.300009
C -1.560783 2.557481 -2.143822
H -2.634686 2.723359 -2.241284
C -0.668367 3.361796 -2.874526
H -1.047524 4.143755 -3.531321
C 0.707087 3.155625 -2.756012
H 1.398005 3.779032 -3.322962
C 1.212652 2.152443 -1.913669
H 2.287703 1.999963 -1.829639
C 3.351049 -0.328102 0.135256
C 4.102494 0.572922 0.925770
C 5.478612 0.714003 0.720787
H 6.037070 1.413776 1.343199
C 6.155851 -0.016294 -0.260354
C 5.409771 -0.905862 -1.035140
H 5.922842 -1.482772 -1.805953
C 4.031844 -1.073583 -0.852372
C 3.418922 1.391487 2.014448
H 2.347031 1.154846 1.968898
C 3.912033 1.003322 3.415537
H 4.980965 1.223385 3.539391
H 3.363596 1.559890 4.187159
H 3.764526 -0.066593 3.599903
C 3.555414 2.902169 1.780610
H 2.995153 3.461777 2.541319
H 4.603667 3.225491 1.834168
H 3.163597 3.183739 0.797241
C 7.650748 0.140561 -0.483914
H 7.921530 -0.525922 -1.316399
C 8.027161 1.569688 -0.900811
H 9.101289 1.644943 -1.118787
H 7.472360 1.877975 -1.794333
H 7.796987 2.288169 -0.104367
C 8.465520 -0.302463 0.740184
H 9.543683 -0.239567 0.538509
H 8.249825 0.332515 1.608473
H 8.227007 -1.335435 1.018541
C 3.271583 -2.054846 -1.735737
H 2.228060 -2.054610 -1.392332
C 3.262722 -1.611827 -3.205622
H 4.278615 -1.592379 -3.622918
H 2.662956 -2.301520 -3.814447
H 2.834550 -0.609075 -3.309715
C 3.795359 -3.490607 -1.596108
H 3.182784 -4.183689 -2.187795
H 4.831892 -3.578529 -1.948406
H 3.765443 -3.819541 -0.551245
B 1.790057 -0.499976 0.354855
211
C -0.303127 0.448755 1.295504

H -0.688985 1.042399 2.141601
C 0.023153 1.352192 0.060463
H 0.035276 2.421288 0.332620
C -1.067591 1.098992 -0.953208
C -1.938669 0.047967 -0.572253
C -3.007038 -0.307398 -1.416735
H -3.680729 -1.109946 -1.123930
C -3.210934 0.376290 -2.611043
H -4.039493 0.113082 -3.263195
C -2.343241 1.419054 -2.972500
H -2.509839 1.953446 -3.905068
C -1.271852 1.784163 -2.155805
H -0.606414 2.589946 -2.454616
C 0.994208 -0.214996 1.692784
C 2.044506 0.039493 0.776345
C 3.318297 -0.511307 1.010618
H 4.128021 -0.310584 0.312323
C 3.545079 -1.291948 2.139545
H 4.528664 -1.712463 2.331418
C 2.496624 -1.530436 3.042144
H 2.680480 -2.136867 3.926154
C 1.223000 -1.001291 2.827276
H 0.421606 -1.201661 3.533786
C -2.160944 -1.689948 1.609206
C -1.790708 -3.029083 1.335085
C -2.376469 -4.073219 2.057015
H -2.082788 -5.096984 1.836626
C -3.330556 -3.839735 3.053673
C -3.696251 -2.516201 3.306646
H -4.445126 -2.319811 4.071951
C -3.134206 -1.443582 2.603747
C -0.778616 -3.350898 0.233934
H -0.341462 -2.401083 -0.105785
C 0.389862 -4.224018 0.726144
H 1.124378 -4.363553 -0.076026
H 0.047597 -5.218814 1.034898
H 0.899431 -3.760579 1.576367
C -1.466081 -3.991589 -0.987493
H -0.738264 -4.185693 -1.785038
H -2.246556 -3.338266 -1.391536
H -1.933072 -4.946882 -0.719191
C -3.957967 -4.983757 3.840032
H -4.677845 -4.536356 4.539400
C -2.913509 -5.743131 4.680169
H -3.393518 -6.523204 5.283600
H -2.382540 -5.065498 5.357765
H -2.165838 -6.228807 4.041769
C -4.741470 -5.948958 2.930532
H -5.234683 -6.727335 3.525338
H -4.078457 -6.448684 2.214335
H -5.509954 -5.417647 2.358447
212
C -3.601595 -0.020565 2.912120
H -3.061170 0.664066 2.244021
C -5.100490 0.169989 2.611197
H -5.401631 1.209794 2.787250
H -5.720690 -0.469564 3.249935
H -5.326549 -0.078668 1.568652
C -3.268360 0.400324 4.355766
H -3.566209 1.440372 4.536347
H -2.194726 0.312810 4.557733
H -3.794046 -0.227603 5.084634
C 2.337248 1.477207 -1.603387
C 2.457851 0.672012 -2.761963
C 3.179901 1.142770 -3.862800
H 3.265498 0.512968 -4.745524
C 3.795906 2.399244 -3.861434
C 3.679240 3.179579 -2.709290
H 4.161531 4.155256 -2.690107
C 2.969592 2.741130 -1.584938
C 1.830437 -0.722122 -2.814278
H 1.201904 -0.840057 -1.920016
C 0.908822 -0.920124 -4.031473
H 0.425214 -1.903304 -3.987038
H 1.468811 -0.871698 -4.972808
H 0.125073 -0.157156 -4.062537
C 2.906875 -1.823596 -2.756061
H 2.444910 -2.818605 -2.759395
H 3.516688 -1.735008 -1.850829
H 3.578197 -1.762362 -3.620986
C 4.571645 2.908141 -5.069714
H 4.959330 3.902359 -4.807493
C 3.664477 3.079345 -6.302993
H 4.227699 3.503215 -7.143294
H 2.822484 3.745456 -6.084938
H 3.252324 2.117272 -6.629960
C 5.783191 2.014742 -5.396486
H 6.360905 2.434482 -6.228934
H 5.467210 1.005774 -5.687081
H 6.449135 1.919286 -4.531907
C 2.902158 3.634827 -0.346017
H 2.364468 3.082831 0.437256
C 2.113743 4.930935 -0.612862
H 2.039362 5.536902 0.298390
H 1.097830 4.714045 -0.962334
H 2.603941 5.541094 -1.380638
C 4.299328 3.944605 0.224422
H 4.217389 4.531528 1.147196
H 4.903698 4.522492 -0.484305
H 4.844031 3.022467 0.454130
B -1.514975 -0.497108 0.811280
B 1.534285 0.969380 -0.348282
213
Table B-6 Optimized x,y,z coordinates for 3-7Tip (trans isomer) calculated on Gaussian 09 at the B3LYP//6-
31g(d) level
C -0.666749 -0.565743 -0.152445

C 0.370214 0.565889 0.132982
H -0.086198 1.145290 0.968496
C 0.271443 1.475015 -1.064583
C -0.991640 1.307171 -1.703336
C -1.325016 2.137345 -2.783095
H -2.291076 2.028244 -3.271983
C -0.416721 3.095059 -3.238544
H -0.669777 3.733219 -4.081264
C 0.825738 3.234640 -2.609969
H 1.527866 3.982486 -2.971198
C 1.176507 2.432244 -1.517510
H 2.138377 2.559962 -1.027558
C -0.567769 -1.474981 1.045031
C 0.695987 -1.307926 1.682756
C 1.029997 -2.138976 2.761632
H 1.996635 -2.030743 3.249558
C 0.121637 -3.096441 3.217526
H 0.375252 -3.735207 4.059617
C -1.121581 -3.234917 2.590258
H -1.823795 -3.982486 2.951881
C -1.472983 -2.431796 1.498511
H -2.435491 -2.558688 1.009575
C -3.279628 -0.293460 -1.277924
C -3.658060 -1.115016 -2.365139
C -5.000610 -1.472221 -2.526819
H -5.279749 -2.113591 -3.359776
C -5.995428 -1.030108 -1.647591
C -5.608665 -0.213386 -0.582058
H -6.372704 0.143605 0.106092
C -4.274002 0.155075 -0.380748
C -2.609652 -1.651623 -3.339916
H -1.659929 -1.144506 -3.119768
C -2.377143 -3.162124 -3.138657
H -1.585491 -3.527462 -3.804265
H -3.288321 -3.732050 -3.356489
H -2.085650 -3.385373 -2.106188
C -2.943236 -1.336279 -4.809508
H -2.134530 -1.675455 -5.467837
H -3.077967 -0.259971 -4.962912
H -3.862926 -1.837622 -5.132411
C -7.456027 -1.418994 -1.839139
H -8.022703 -0.954009 -1.020599
C -7.665336 -2.941607 -1.735099
H -8.729513 -3.193416 -1.818547
H -7.297020 -3.326867 -0.777973
H -7.134431 -3.472296 -2.534450
C -8.027208 -0.872279 -3.161307
H -9.093927 -1.111031 -3.251101
H -7.514697 -1.308522 -4.027013
214
H -7.914083 0.215725 -3.220845
C -3.901469 1.073177 0.783131
H -2.802233 1.136740 0.817219
C -4.424120 2.505409 0.558866
H -4.110109 3.167448 1.375015
H -5.519648 2.520859 0.515967
H -4.046251 2.919690 -0.382096
C -4.353145 0.521082 2.147184
H -4.017412 1.178197 2.958310
H -3.939945 -0.477289 2.325279
H -5.445250 0.451664 2.209707
C 2.984264 0.292707 1.253094
C 3.974962 -0.143667 0.342187
C 5.308792 0.225603 0.533762
H 6.061990 -0.125511 -0.168214
C 5.700943 1.034133 1.607139
C 4.713101 1.460749 2.497582
H 5.005287 2.092862 3.333998
C 3.367903 1.101865 2.344870
C 3.593615 -1.055034 -0.824601
H 2.493894 -1.109224 -0.857774
C 4.047825 -0.505070 -2.188509
H 3.702241 -1.156689 -2.999895
H 5.140443 -0.448264 -2.254824
H 3.645542 0.498268 -2.363496
C 4.104191 -2.492149 -0.603156
H 3.784317 -3.150244 -1.420236
H 3.723343 -2.904806 0.337317
H 5.199597 -2.516590 -0.560539
C 7.155584 1.440553 1.806951
H 7.193412 2.069277 2.707300
C 7.682773 2.287190 0.632907
H 8.711014 2.617469 0.823935
H 7.062034 3.176141 0.475917
H 7.685987 1.713445 -0.301551
C 8.063780 0.222176 2.059110
H 9.093926 0.541029 2.259174
H 8.085226 -0.444659 1.188918
H 7.713861 -0.361502 2.917580
C 2.328449 1.625698 3.335534
H 1.375906 1.124072 3.115046
C 2.097715 3.139697 3.159871
H 1.311925 3.495841 3.837296
H 1.798588 3.379888 2.133387
H 3.011567 3.704512 3.379753
C 2.674080 1.287251 4.797240
H 1.872148 1.618393 5.467837
H 3.598037 1.781403 5.119038
H 2.807346 0.208411 4.933247
B -1.787206 0.130213 -1.032673
B 1.491356 -0.131022 1.011673
H -0.209606 -1.145274 -0.987498
215
K 0.597814 2.861744 -0.035602

O 0.777740 4.514110 -2.254842
O -1.223264 4.123754 1.631931
O 2.948429 4.266844 0.487679
B -1.738002 0.452772 -1.122863
C -0.676671 0.044877 -0.100400
C -1.781655 -0.210905 0.885661
C -1.998451 -0.669148 2.173509
H -1.187835 -0.938282 2.843498
C -3.356008 -0.728833 2.627032
H -3.560676 -1.060869 3.642470
C -4.401240 -0.362414 1.807699
H -5.421612 -0.412624 2.180124
C -4.159013 0.085741 0.467190
H -5.005009 0.361136 -0.158342
C -2.858534 0.155541 0.019198
C -1.893057 0.941355 -2.630053
C -1.381059 0.199226 -3.737440
C -1.576999 0.645198 -5.045804
H -1.181571 0.058415 -5.867695
C -2.284835 1.812772 -5.340980
C -2.809310 2.523867 -4.267129
H -3.381016 3.425950 -4.473392
C -2.635381 2.114008 -2.939766
C -0.716090 -1.160843 -3.520158
H -0.164811 -1.104833 -2.579114
C 0.282768 -1.572347 -4.610078
H -0.203231 -1.767228 -5.570974
H 0.784286 -2.499233 -4.320193
H 1.052449 -0.813069 -4.765566
C -1.792838 -2.252386 -3.365194
H -2.483405 -2.019544 -2.551774
H -1.330008 -3.224292 -3.158604
H -2.381214 -2.350353 -4.283535
C -2.511765 2.272701 -6.774195
H -3.043289 3.231250 -6.721751
C -3.412316 1.295374 -7.551317
H -3.618805 1.669517 -8.559477
H -4.367853 1.149510 -7.041231
H -2.939040 0.314111 -7.652636
C -1.195744 2.521495 -7.531067
H -0.614736 1.601196 -7.640776
H -0.567717 3.246954 -7.007088
H -1.391141 2.908664 -8.536329
C -3.297344 2.961562 -1.854387
H -3.013069 2.535555 -0.890547
C -2.832291 4.429212 -1.867915
H -1.744657 4.512587 -1.810134
H -3.260716 4.975471 -1.020916
H -3.153387 4.946514 -2.777745
C -4.832432 2.888457 -1.949908
H -5.197016 3.354099 -2.871256
216
H -5.303217 3.406839 -1.107906
H -5.179643 1.853612 -1.944023
C 0.775448 4.041649 -3.612626
H 0.008206 3.273556 -3.694390
H 1.752774 3.595843 -3.835828
C 0.513627 5.286908 -4.480429
H 1.106782 5.263517 -5.396939
H -0.536602 5.341695 -4.770629
C 0.896937 6.475663 -3.558082
H 0.020260 7.086146 -3.331517
H 1.648040 7.131821 -4.003368
C 1.421293 5.789672 -2.287174
H 2.509980 5.650485 -2.330631
H 1.176997 6.310196 -1.360654
C -2.457064 3.505724 2.086757
H -2.244092 2.913606 2.980327
H -2.810650 2.829378 1.309892
C -3.406063 4.661426 2.392019
H -4.157901 4.393930 3.136963
H -3.928431 4.982497 1.485979
C -2.437989 5.752419 2.871190
H -2.842411 6.762974 2.781530
H -2.169675 5.589417 3.919455
C -1.225328 5.525091 1.964702
H -1.304801 6.107061 1.038515
H -0.275836 5.771627 2.448321
C 4.112079 3.796179 -0.214405
H 3.857850 2.860282 -0.709095
H 4.393958 4.537198 -0.976153
C 5.201681 3.659915 0.858402
H 6.191644 3.886797 0.457422
H 5.226284 2.638506 1.240086
C 4.761846 4.656891 1.963974
H 5.492772 5.451879 2.127622
H 4.617477 4.141654 2.914908
C 3.428244 5.220583 1.438280
H 2.662988 5.339707 2.206557
H 3.576832 6.189290 0.939594
B 1.767307 -0.532180 1.171157
C 0.724226 -0.116413 0.134251
C 1.847260 0.154533 -0.827410
C 2.093248 0.639536 -2.100411
H 1.298733 0.923980 -2.783576
C 3.460094 0.704219 -2.524178
H 3.686279 1.054309 -3.528934
C 4.488044 0.323394 -1.689901
H 5.515838 0.378790 -2.040307
C 4.217241 -0.145677 -0.362168
H 5.049281 -0.427288 0.279347
C 2.907684 -0.225516 0.054746
C 1.886292 -1.022801 2.681263
C 1.427954 -0.234813 3.778715
C 1.578258 -0.685993 5.091210
H 1.222604 -0.065665 5.906861
217
C 2.191166 -1.903641 5.396938
C 2.669559 -2.658751 4.331483
H 3.172425 -3.598627 4.547684
C 2.537814 -2.243546 3.000743
C 0.880078 1.172342 3.540899
H 0.322329 1.145504 2.601705
C -0.076545 1.689636 4.622910
H 0.425340 1.855897 5.581116
H -0.491667 2.652898 4.314653
H -0.910415 1.003674 4.789939
C 2.049818 2.160216 3.363201
H 2.709983 1.853979 2.548925
H 1.679550 3.168186 3.144543
H 2.650618 2.215379 4.277115
C 2.370855 -2.371924 6.834100
H 2.830015 -3.367609 6.790989
C 3.334869 -1.460372 7.614969
H 3.506550 -1.845456 8.625555
H 4.301949 -1.386321 7.111234
H 2.934066 -0.446771 7.710496
C 1.033006 -2.517692 7.579625
H 0.522715 -1.555329 7.679904
H 0.356451 -3.195962 7.052699
H 1.189390 -2.913636 8.588249
C 3.157386 -3.128429 1.920293
H 2.866695 -2.709857 0.953968
C 2.659412 -4.584221 1.963900
H 1.569529 -4.645356 1.924890
H 3.061562 -5.152178 1.118383
H 2.985012 -5.096270 2.874950
C 4.695086 -3.089632 1.991263
H 5.059997 -3.542517 2.918885
H 5.141568 -3.638787 1.155446
H 5.066149 -2.064044 1.955423
K -0.628726 -2.924311 0.053637
O -0.924838 -4.584155 2.261190
O 1.233686 -4.223497 -1.548833
O -3.019389 -4.233225 -0.530633
C -0.970786 -4.103022 3.615701
H -0.175713 -3.368224 3.731851
H -1.936687 -3.612080 3.785511
C -0.807865 -5.351529 4.503872
H -1.459918 -5.302373 5.378414
H 0.217888 -5.440568 4.864872
C -1.169911 -6.532705 3.563598
H -0.295904 -7.161584 3.380925
H -1.956128 -7.172500 3.970400
C -1.612889 -5.836721 2.268249
H -2.696990 -5.660504 2.261582
H -1.344543 -6.370129 1.355714
C 2.486714 -3.640947 -1.996123
H 2.302565 -3.067470 -2.908251
H 2.839601 -2.951835 -1.230095
C 3.418187 -4.821510 -2.256669
218
H 4.189198 -4.586150 -2.992847
H 3.916821 -5.131785 -1.333713
C 2.437091 -5.903480 -2.729823
H 2.819043 -6.919686 -2.610694
H 2.191230 -5.758112 -3.786148
C 1.212832 -5.631797 -1.851674
H 1.262689 -6.194198 -0.911569
H 0.267631 -5.869501 -2.347970
C -4.186373 -3.758773 0.162633
H -3.919144 -2.849982 0.699059
H -4.508333 -4.521332 0.886532
C -5.241044 -3.548844 -0.930981
H -6.251400 -3.732997 -0.559985
H -5.202982 -2.519781 -1.290750
C -4.821529 -4.543929 -2.045601
H -5.568544 -5.323067 -2.212893
H -4.670569 -4.025223 -2.993652
C -3.498793 -5.141390 -1.525857
H -2.725742 -5.235827 -2.289460
H -3.662502 -6.127995 -1.069152
K 0.593638 -0.113455 -2.769916

O -0.356287 1.102771 -4.994590
O 2.709095 -1.715792 -3.410409
C -0.672637 -0.242846 -0.196504
C -1.438789 0.905129 -0.654753
C -0.644887 2.113122 -0.559691
C -1.222484 3.324810 -0.963248
H -0.642422 4.244119 -0.899073
C -2.536209 3.378636 -1.442462
H -2.971956 4.328654 -1.740893
C -3.294954 2.202775 -1.532903
H -4.316186 2.247957 -1.903785
C -2.753169 0.973684 -1.149235
H -3.352250 0.069288 -1.224776
C -1.954672 -2.770562 -0.350577
C -3.130000 -2.868394 0.444032
C -4.118104 -3.809771 0.150278
H -5.000127 -3.865563 0.781016
C -4.011781 -4.684228 -0.933086
C -2.870132 -4.583428 -1.720664
H -2.773306 -5.246709 -2.577181
C -1.854281 -3.659492 -1.448518
C -3.303856 -1.975850 1.672001
H -2.748345 -1.057881 1.456074
C -2.679178 -2.640303 2.914321
H -3.195714 -3.575571 3.151295
H -2.756800 -1.992885 3.797260
219
H -1.626182 -2.884627 2.750579
C -4.752644 -1.557845 1.962973
H -4.774013 -0.802022 2.754716
H -5.369014 -2.394188 2.305973
H -5.230632 -1.130727 1.077863
C -5.094384 -5.706476 -1.248416
H -4.766797 -6.253695 -2.141262
C -6.439818 -5.042097 -1.589194
H -7.185072 -5.791226 -1.875975
H -6.333070 -4.336628 -2.417334
H -6.840255 -4.488772 -0.734593
C -5.260572 -6.737748 -0.118469
H -5.996803 -7.501527 -0.389498
H -5.601788 -6.264047 0.806913
H -4.314635 -7.240740 0.098489
C -0.664253 -3.603148 -2.404574
H 0.076021 -2.935554 -1.954113
C -1.073824 -3.009009 -3.765597
H -1.777316 -3.662313 -4.290209
H -0.202992 -2.874747 -4.417878
H -1.573560 -2.042396 -3.645185
C 0.030110 -4.961456 -2.593015
H 0.914296 -4.854924 -3.230066
H -0.625703 -5.697388 -3.067360
H 0.354018 -5.372979 -1.634288
C -1.698019 1.626986 -4.997249
H -2.078981 1.577952 -3.977966
H -2.322429 0.997439 -5.644796
C -1.581642 3.059894 -5.548346
H -2.414575 3.296703 -6.213508
H -1.592611 3.785203 -4.734069
C -0.215826 3.069544 -6.286722
H 0.487862 3.737226 -5.786088
H -0.297611 3.394234 -7.326155
C 0.260775 1.613860 -6.180411
H -0.066145 1.021764 -7.046892
H 1.340650 1.504263 -6.070616
C 3.510103 -2.322388 -2.373466
H 2.891500 -2.411856 -1.482727
H 4.353955 -1.660612 -2.146988
C 3.991993 -3.665495 -2.953547
H 3.402563 -4.494736 -2.560773
H 5.034842 -3.853694 -2.690962
C 3.790742 -3.513608 -4.484984
H 4.696687 -3.728459 -5.055595
H 3.009982 -4.189159 -4.840948
C 3.347472 -2.052936 -4.645398
H 4.210601 -1.391628 -4.806855
H 2.628038 -1.889610 -5.449625
B -0.778572 -1.731777 -0.026639
C 0.672620 0.242865 0.196534
C 1.438772 -0.905111 0.654781
C 0.644871 -2.113102 0.559719
C 1.222471 -3.324795 0.963273
220
H 0.642408 -4.244100 0.899097
C 2.536196 -3.378618 1.442485
H 2.971945 -4.328636 1.740913
C 3.294940 -2.202756 1.532926
H 4.316172 -2.247940 1.903805
C 2.753152 -0.973665 1.149260
H 3.352235 -0.069269 1.224802
C 1.954660 2.770576 0.350599
C 3.129987 2.868405 -0.444014
C 4.118094 3.809783 -0.150260
H 5.000113 3.865578 -0.781001
C 4.011775 4.684238 0.933107
C 2.870129 4.583435 1.720689
H 2.773308 5.246717 2.577207
C 1.854273 3.659502 1.448543
C 3.303830 1.975862 -1.671984
H 2.748329 1.057892 -1.456049
C 2.679135 2.640308 -2.914298
H 3.195671 3.575572 -3.151291
H 2.756736 1.992884 -3.797236
H 1.626143 2.884642 -2.750539
C 4.752613 1.557850 -1.962979
H 4.773966 0.802009 -2.754707
H 5.368973 2.394185 -2.306015
H 5.230623 1.130752 -1.077872
C 5.094378 5.706483 1.248434
H 4.766794 6.253703 2.141279
C 6.439812 5.042102 1.589210
H 7.185071 5.791232 1.875989
H 6.333068 4.336632 2.417350
H 6.840247 4.488775 0.734608
C 5.260570 6.737756 0.118487
H 5.996799 7.501530 0.389516
H 5.601784 6.264055 -0.806895
H 4.314633 7.240752 -0.098471
C 0.664251 3.603159 2.404604
H -0.076027 2.935569 1.954140
C 1.073826 3.009006 3.765622
H 1.777322 3.662302 4.290232
H 0.202997 2.874742 4.417906
H 1.573556 2.042391 3.645199
C -0.030105 4.961466 2.593058
H -0.914293 4.854933 3.230109
H 0.625712 5.697392 3.067406
H -0.354015 5.372999 1.634336
B 0.778557 1.731795 0.026666
K -0.593669 0.113485 2.769944
O 0.356237 -1.102786 4.994607
O -2.709121 1.715833 3.410429
C 1.697966 -1.627010 4.997253
H 2.078927 -1.577958 3.977971
H 2.322379 -0.997479 5.644812
C 1.581582 -3.059932 5.548320
H 2.414497 -3.296746 6.213499
221
H 1.592577 -3.785224 4.734030
C 0.215748 -3.069606 6.286660
H -0.487933 -3.737257 5.785974
H 0.297503 -3.394345 7.326079
C -0.260839 -1.613912 6.180402
H 0.066086 -1.021854 7.046910
H -1.340711 -1.504299 6.070606
C -3.510110 2.322442 2.373482
H -2.891509 2.411881 1.482740
H -4.353985 1.660691 2.147012
C -3.991955 3.665569 2.953550
H -3.402461 4.494778 2.560805
H -5.034782 3.853828 2.690924
C -3.790767 3.513663 4.484996
H -4.696738 3.728506 5.055570
H -3.010027 4.189213 4.841000
C -3.347505 2.052987 4.645412
H -4.210638 1.391685 4.806869
H -2.628077 1.889662 5.449647
222
APPENDIX C: LIST OF PUBLICATIONS
To date, two publications from this work have appeared in peer-reviewed journals. R1 is
comprised of results from Chapter 2, while R2 outlines results from Chapter 3. The compounds
discussed in Chapter 4, will constitute a third publication, currently in preparation. The author
was responsible for all material in publications R1 and R2 with the exception of X-ray crystal
data collection and analysis. In publication R1, Dr. Benedikt Neue was responsible for the
theoretical calculations. Collaboration to another research project in the Piers group gave rise to
article R3, where most contributions were through photophysical experiments and analysis of
results. Finally, another article was published highlighting the stabilization of boron-containing
molecules via encasing the boron in a rigid, planarized environment.
R1. Araneda, J. F.; Neue, B.; Piers, W. E.; Parvez, M. Angew. Chem. Int. Ed. 2012, 51, 8546.
R2. Araneda, J. F.; Piers, W. E.; Sgro, M. J.; Parvez, M. Chem. Sci. 2014, 5, 3189.
R3. Neue, B.; Araneda, J. F.; Piers, W. E.; Parvez, M. Angew. Chem. Int. Ed. 2013, 52, 9966.
R4. Araneda, J. F.; Neue, B.; Piers, W. E. Angew. Chem. Int. Ed. 2012, 51, 9977.
223
APPENDIX D: COPYRIGHT PERMISSION
224
225
226
227
228
229
230
231
232
233
From: Warren Edward Piers wpiers@ucalgary.ca
Subject: Permission
Date: April 2, 2015 at 1:12 PM
To: Juan Felipe Araneda jfaraned@gmail.com
I, Warren Edward Piers, give permission to Juan Araneda-Arango to include the material published in the
journals Angewandte Chemie International Edition (vol 51, pages 8546-8550) and Chemical Science (vol 5,
pages 3189-3196) in his Ph.D. thesis entitled "Synthesis, Characterization and Reactivity of π-Conjugated
Organoboron Compunds", where I am a co-author.
Warren E. Piers, Ph. D. FRSC, FCIC

Tier I Canada Research Chair in the Mechanisms of Homogeneous Catalytic Reactions
Associate Editor, Dalton Transactions
University of Calgary, Department of Chemistry
2500 University Dr. NW
Calgary, Alberta T2N 1N4
403-220-5746
FAX: 403-289-9488
http://www.ucalgary.ca/wpiers/
234
From: Masood Parvez parvez@ucalgary.ca
Subject: RE: thesis
To: Juan Felipe Araneda jfaraned@gmail.com
Hello Juan Felipe Araneda
I, Masood Parvez, give permission to Juan Araneda-Arango to include the material published in the journals
Angewandte Chemie International Edition (vol 51, pages 8546-8550) and Chemical Science (vol 5, pages
3189-3196) in his Ph.D. thesis entitled "Synthesis, Characterization and Reactivity of π-Conjugated
Organoboron Compunds", where I am a co-author.
With best wishes.
Masood Parvez
From: Juan Felipe Araneda [jfaraned@gmail.com]

Sent: Thursday, April 02, 2015 1:10 PM
To:From:
WarrenMichael
EdwardSgro
Piers;mjsgro@ucalgary.ca
Masood Parvez
Subject:
Subject: thesis
RE: Content Permission Request
To: Juan
Hi Warren andFelipe Araneda [jfaraned@gmail.com] jfaraned@gmail.com
Masood,
IToamwhom
about ittoconcerns,
submit my thesis to FGS, but because some of the chemistry described in the thesis was already published,
and you are a co-authors, I need your permission to include the co-authored material in my thesis. The permission is
I, Michael
quite Sgro,
informal, give
I just permission
need to me
you to send Juan Araneda-Arango
an email saying that I to
aminclude
allowedthe material
to use published
the chemistry in papers.
of the the journal
You can
use this template, just put your name where it says "co-author name". Please don't reply to this email, send me and
Chemical Science (vol 5, pages 3189-3196) in his Ph.D. thesis entitled "Synthesis, Characterization a new
Reactivity
email of π-Conjugated
with the authorization. Organoboron Compunds", where I am a co-author.
Sincerely,
I, co-author name, give permission to Juan Araneda-Arango to include the material published in the journals
Angewandte Chemie International Edition (vol 51, pages 8546-8550) and Chemical Science (vol 5, pages 3189-3196) in
Michael
his Ph.D.Sgro
thesis entitled "Synthesis, Characterization and Reactivity of π-Conjugated Organoboron Compunds", where I
am a co-author.
From: Benedikt Neue neuebenedikt@gmail.com

Thanks!!
Subject: Permission to include published material
To: Juan Araneda jfaraned@gmail.com
I, Benedikt Neue, give permission to Juan Araneda-Arango to include the material published in the journal Angewandte Chemie International
Edition (vol 51, pages 8546-8550) in his Ph.D. thesis entitled "Synthesis, Characterization and Reactivity of π-Conjugated Organoboron
Compunds", where I am a co-author.
Dr. Benedikt Neue

Dieckmannstraße 154
48161 Münster
+ 49 176/21989887
neuebenedikt@gmail.com
235

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PRISM: University of Calgary's Digital Repository

Graduate Studies The Vault: Electronic Theses and Dissertations

Synthesis, Characterization and Reactivity of

Araneda Arango, Juan

Araneda Arango, J. (2015). Synthesis, Characterization and Reactivity of Pi-Conjugated

Synthesis, Characterization and Reactivity of Pi-Conjugated Organoboron Compounds

Juan Felipe Araneda Arango

SUBMITTED TO THE FACULTY OF GRADUATE STUDIES

IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE

DEGREE OF DOCTOR OF PHILOSOPHY

GRADUATE PROGRAM IN CHEMISTRY

© Juan Felipe Araneda Arango 2015

candidates because the annelation eliminates conformational disorders, leading to attractive

application in optoelectronics. Arguably the most important characteristic of a three-coordinate

also alter the electronic characteristics of a compound significantly.

dioxide was also investigated.

Many thanks are extended to members of my defence committee: Dr. Thomas

who served as my external examiner.

CHAPTER ONE: INTRODUCTION ................................................................................. 1

CHAPTER TWO: TOWARDS THE SYNTHESIS OF BENZOBOROLE-FUSED

CHAPTER THREE: BRØNSTED ACID-CATALYZED SKELETAL

CHAPTER FOUR: BOROLE RING-EXPANSION BY ADDITION OF CO AND CO293

CHAPTER FIVE: CONCLUSIONS AND FUTURE WORK ....................................... 120

CHAPTER SIX: EXPERIMENTAL DETAILS ............................................................. 131

REFERENCES ................................................................................................................ 153

APPENDIX A: CRYSTALLOGRAPHIC DATA .......................................................... 163

APPENDIX B: THEORETICAL CALCULATIONS .................................................... 204

APPENDIX C: LIST OF PUBLICATIONS ................................................................... 223

APPENDIX D: COPYRIGHT PERMISSION ............................................................... 224

Table 2-1 Selected Metrical Data for 2-3Tip .................................................................................. 29

Table 3-1 Selected Metrical Data for 3-1Tip .................................................................................. 59

Table 3-2 Electrochemical data for 2-4Tip and 2-5Tip .................................................................... 61

Table 3-4 Selected Metrical Data for 3-4Tip .................................................................................. 67

Table 3-5 Selected Metrical Data for 3-5Tip .................................................................................. 75

Table 3-6 Selected Metrical Data for 3-6Tip .................................................................................. 76

Table 3-8 Selected Metrical Data for 3-7Tip .................................................................................. 84

Table 4-1 Selected Metrical Data for 4-1Tip ................................................................................ 102

Table 4-2 Selected Metrical Data for 4-2Tip ................................................................................ 111

Figure 1-1 Calculated electronic structures of parent polyheteroles. .............................................. 2

Figure 1-3 Ladder compounds containing the thiophene unit......................................................... 4

Figure 1-4 Functional features of boron.......................................................................................... 6

Figure 1-5 Anthacene (left) and boraanthacene (right) ................................................................... 6

Figure 1-6 Boron-containing heterocycles ...................................................................................... 7

Figure 1-7 Several borole derivatives ............................................................................................. 8

Figure 1-8 Dibenzoborole and benzoborole-fused benzoheteroles compounds ............................. 9

Figure 1-10 Examples of aromatic and antiaromatic compounds ................................................. 17

Figure 1-11 Magnetic shielding lines for benzene ........................................................................ 18

Figure 2-8 Photochemical reaction of 2-4Tip monitored by 1H NMR spectroscopy (irradiated

Figure 2-11 Chemical shift of isopropyl methine protons ............................................................ 46

Figure 3-6 11B chemical shifts of several borole dianions ............................................................ 72

Figure 3-15 1H NMR spectrum of compound 3-7Tip (CD2Cl2, 600 MHz).................................... 86

Figure 3-16 Isomerization of 3-5Tip to 3-6Tip after addition of 2 equivalents of t-butanol

Figure 4-5 Absorption spectrum of compound 4-1Tip in CH2Cl2 ................................................ 104

Figure 4-6 Emission spectrum of compound 4-1Tip in CH2Cl2 ................................................... 105

Figure 4-10 Absorption spectrum of compound 4-2Tip in THF .................................................. 113

Figure 4-12 Emission spectrum of compound 4-2Tip in THF ..................................................... 115

Figure 5-1 Organometallic polymer ............................................................................................ 123

Figure 5-3 4-1Tip and BINOL compounds .................................................................................. 129

Figure 5-4 Heterobimetallic multifunctional catalyst using cerium............................................ 129

Figure 6-1 Photochemical reaction of 2-4Tip monitored by 1H NMR spectroscopy. Alkyl

Scheme 1-1 Synthesis of benzoheterole-fused benzoheterole derivatives ...................................... 4

Scheme 1-2 Synthesis of benzosilole-fused benzosilole derivatives .............................................. 4