Periodic Table of the Elements with the Gmelin System Numbers

I l
I
I
2
H 2 I ~2 He l
!
I!
3 4 5 6 7 10 I
Li 20 Be 26 B 13 c 14 N4 g3 ~5 Ne
>
II 21 12 13 14 17 6 18 I
J Na Mg 27 Al 35 Si 15 ~5 16 ~6 9 Cl Ar
s
i 20 21 22 23 24 25 26 27 28 29 30 31 32 33
C) 19 22 34 10 35 7 as 1
i.:r K Ca 28 Sc 39 Jj 41 v 48 Cr 52 Mn 56 Fe 59 Co 58 Ni 57 Cu 60 Zn 32 Ga 36 Ge45 As 17 Se Br Kr

37 24 38 39 40 41 42 43 44 45 46 47 48 49 50 52 11 54 1
Sr 29 y 39 Zr 42 Nb49 Mo 53 Tc 69 Ru 63 Rh 64 Pd 65 Ag 61 Cd 33 In 37 sn 46 ~~ 18 513 8
Rb Te Xe
iii"
f...
~- 55 ?5 56 30 57** 72 73 74 75 76 77 78 79 80 81 82 84 12 85 as
Cs ·· Ba La 39 Hf 43 Ta 50 w 54 Re 70 Os 66 lr 67 Pt 68 Au 62 Hg34 Tl 38 Pb 47 :~ 19 Po At 8a Rn 1
!l
i 87 88 31 89*** 104 71 105 71
~ Fr 25a Ra Ac 40
i I~H.''i
i
'**Lanthanides 58 59 60 61 62 63 64 65 66 67 68 69 70 71
i 39 Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

'***Actin ides 90 -l 91 92 93 94 7 95 96 71 97 98 99 100 7 101 102 71 103 7 1

Th Pa u Np Pu Am Cm Bk Cf Es Fm Md No Lr
Gmelin Handbook of Inorganic Chemistry

8th Edition
Gmelin Handbook
of Inorganic Chemistry
8th Edition

Gmelin Handbuch der Anorganischen Chemie

Achte, voLLig neu bearbeitete Auflage

Prepared Gmelin-lnstitut fOr Anorganische Chemie

and issued by der Max-Planck-Gesellschaft
zur Forderung der Wissenschaften
Director: Ekkehard Fluck

Founded by Leopold Gmelin

8th Edition 8th Edition begun under the auspices of the
Deutsche Chemische Gesellschaft by A. J. Meyer
Continued by E.H.E. Pietsch and A. Kotowski, and by
Margot Becke- Goehring

Springer-Verlag Berlin Heidelberg GmbH 1987

Gmelin-lnstitut fUr Anorganische Chemie
der Max-Planck-Gesellschaft zur Forderung der Wissenschaften

ADVISORY BOARD

Dr. G. Breil, Chairman (Ruhrchemie AG, Oberhausen-Holten), Prof. Dr. K. Dehnicke (Philipps-
Universitat, Marburg), Prof. Dr. N. N. Greenwood (University of Leeds), Prof. Dr. H. Grunewald
(Bayer AG, Leverkusen), Prof. Dr. H. Harnisch (Hoechst AG, FrankfurUMain-Hochst), Prof. Dr.
H. Noth (Universitat MOnchen), Prof. Dr. H. Offermanns (Degussa AG, FrankfurUMain), Prof.
Dr. G. zu Putlitz (Universitat Heidelberg), Prof. Dr. A. Rabenau (Max-Planck-InstitutfOr Festkor-
perforschung, Stuttgart), Prof. Dr. A. Simon (Max-Planck-Institut fOr Festkorperforschung,
Stuttgart), Prof. Dr. Dr. A. H. Staab (Prasident der Max-Planck-Gesellschaft, MOnchen), Prof.
Dr. Dr. h.c. mult. G. Wilke (Max-Planck-lnstitut fUr Kohlenforschung, MOlheim/Ruhr)

DIRECTOR DEPUTY DIRECTOR

Prof. Dr. Dr. h.c. Ekkehard Fluck Dr. W. Lippert

CHIEF EDITORS

Dr. K.-C. Buschbeck - Dr. H. Bergmann, J. FOssel, H. Hartwig, B. Heibel, Dr. H. Katscher,
Dr. R. Keirn, Dr. E. Koch, Dipl.-Phys. D. Koschel, Dr. U. KrOerke, Dr. H. K. Kugler, Dr.
P. Merlet, Dr. E. Schleitzer-Rust, Dr. F. SchrOder, Dr. A. Slawisch, Dr. W. Topper

CORRESPONDENT MEMBERS OF THE SCIENTIFIC STAFF Dr. H. C. Andersen, Dr. J. L. Grant,

Dr. V. Haase, Dipl.-lng. G. Kirschstein,
Dr. K. Rumpf, Dr. U. Trobisch,
Dr. B. Vance

EMERITUS MEMBER OF THE INSTITUTE Prof. Dr. Dr. E. h. Margot Becke

CORRESPONDENT MEMBERS OF THE INSTITUTE Prof. Dr. Hans Bock

Prof. Dr. Dr. Alois Haas, Sc. D. (Cantab.)
STAFF GMELIN HANDBOOK

Dr. G. Bar, D. Barthel, Dr. N. Baumann, Dr. W. Behrendt, Dr. L. Berg, Dipl.-Chem. E. Best,
K. D. Bonn, P. Born-Heck, Dipl.-lng. V. A. Chavizon, E. Cloos, Dipl.-Phys. G. Czack, I. Deim,
Dipl.-Chem. H. Demmer, R. Dowideit, Dipl.-Chem. M. DrOBmar, U. Duggen, Dr. P. Eigen,
M. Engels, Dr. H.-J. Fachmann, Dr. J. Faust, Dr. Chr. Fianda, Dr. W.-D. Fleischmann, V.
Frick, G. Funk, Dipl.-lng. N. Gagel, Dr. U. W. Gerwarth, Dipl.-Phys. D. Gras, Dipl.-Bibl.
W. Grieser, Dr. R. Haubold, Dipl.-Min. H. Hein, G. Heinrich-Sterzel, A. Heise-Schuster, H.-P.
Hente, H. W. Herold, U. Hettwer, Dr. W. Hoffmann, Dr. W. Huisl, Dr. S. Jager, Dr. R. Jotter,
Dr. J. von Jouanne, Dr. B. Kalbskopf, Dipl.-Chem. W. Karl, H.-G. Karrenberg, Dipl.-Phys.
H. Keller-Rudek, B. Kirchner, A. Klusch, Dipl.-Phys. E. Koch, Dipl.-Chem. K. Koeber, Dipl.-
Chem. H. Kottelwesch, R. Kolb, E. Kranz, Dipl.-Chem. I. Kreuzbichler, Dr. A. Kubny, Dr.
M. Kunz, Dr. W. Kurtz, M. Langer, Dr. U. Lanzendorfer, Dr. B. Leduc, Dr. A. Leonard, Dipl.-
Chem. H. List, H. Mathis, E. Meinhard, C. Metz, K. Meyer, Dr. M. Mirbach, Dipl.-Chem.
B. Mohsin, Dr. U. Neu-Becker, V. Neumann, K. Noring, Dipl.-Chem. R. Nohl, Dipl.-Min.
U. Nohl, Dr. W. Petz, I. Rangnow, Dipl.-Phys. H.-J. Richter-Ditten, Dipl.-Chem. H. Rieger,
B. Riegert, E. Rieth, A. Rosenberger, E. Rudolph, G. Rudolph, Dipl.-Chem. S. Ruprecht,
Dr. B. Sarbas, V. Schlicht, Dipl.-Chem. D. Schneider, Dipl.-Min. P. Schubert, A. Schwarze!,
Dr. B. Schwager, Dipl.-lng. H.M. Somer, Dr. C. Strametz, Dr. U. Taubald, M. Teichmann,
Dr. D. TiLLe, Dipl.-lng. H. Vanecek, Dipl.-Chem. P. Velie, Dipl.-lng. U. Vetter, H.-M. Wagner,
Dipl.-Phys. J. Wagner, R. Wagner, Dr. E. Warkentin, Dr. C. Weber, Dipl.-Chem. A. Wietel-
mann, Dr. M. Winter, Dr. B. Wobke, K. Wolff

STAFF GMELIN ONLINE DATA SYSTEM

Dr. R. Frobose, Dr. P. Kuhn, Dr. G. Olbrich, Dr. B. Roth

Dr. I. Barthelmess, Dipl.-Min. M.-B. Cinarz, Dr. J. Fippinger, Dr. G. Friedrich, Dr. B. Frohlich,
Dr. M. Kloffler, R. Lohmeyer, Dr. M. Pauluth, Dr. K. Schucke
Organometallic Compounds In the Gmelln Handbook
The following listing indicates in which volumes these compounds are discussed or are
referred to:
Ag Silber B 5 (1975)
Au Organogold Compounds (1980)
Bi Bismut-Organische Verbindungen (1977)
Co Kobalt-Organische Verbindungen 1 (1973), 2 (1973), Kobalt Erg.-Bd. A (1961), B 1
(1963), B 2 (1964)
Cr Chrom-Organische Verbindungen (1971)
Cu Organocopper Compounds 1 (1985), 2 (1983), 3 (1986), 4 (1987) present volume
Fe Eisen-Organische Verbindungen A 1 (1974), A 2 (1977), A 3 (1978), A 4 (1980), A 5
(1981), A 6 (1977), A 7 (1980), A 8 (1985), B 1 (partly in English; 1976), Organoiron
Compounds B 2 (1978), Eisen-Organische Verbindungen B 3 (partly in English;
1979), B 4 (1978), B 5 (1978), Organoiron Compounds B 6 (1981), B 7 (1981), B 8
to B 10 (1985), B 11 (1983), B 12 (1984), Eisen-Organische Verbindungen C 1 (1979),
C 2 (1979), Organoiron Compounds C 3 (1980), C 4 (1981), C 5 (1981), C 7 (1985),
and Eisen B (1929-1932)
Ga Organogallium Compounds 1 (1986)
Hf Organohafnium Compounds (1973)
Nb Niob B 4 (1973)
Ni Nickel-Organische Verbindungen 1 (1975), 2 (1974), Register (1975), Nickel B 3
(1966), and C 1 (1968), C 2 (1969)
Np, Pu Transurane C (partly in English; 1972)
Pt Platin C (1939) and D (1957)
Ru Ruthenium Erg.-Bd. (1970)
Sb Organoantimony Compounds 1 (1981), 2 (1981), 3 (1982), 4 (1986)
Sc, Y, D 6 (1983)
La to Lu
Sn Zinn-Organische Verbindungen 1 (1975), 2 (1975), 3 (1976), 4 (1976), 5 (1978), 6
(1979), Organotin Compounds 7 (1980), 8 (1981), 9 (1982), 10 (1983), 11 (1984),
12 (1985), 13 (1986), 14 (1987)
Ta Tantal B 2 (1971)
Ti Titan-Organische Verbindungen 1 (1977), 2 (1980), Organotitanium Compounds 3
(1984), 4 and Register (1984)
U Uranium Suppl. Vol. E 2 (1980)
V Vanadium-Organische Verbindungen (1971), Vanadium B (1967)
Zr Organozirconium Compounds (1973)
Grnelin Handbook
of Inorganic Chemistry
8th Edition

Cu
Organocopper
Compounds
Part 4

With 86 illustrations

AUTHORS Helmut Bauer, Max-Planck-lnstitut

fOr medizinische Forschung, Heidelberg
JOrgen Faust, Rolf Frobose, Johannes FOssel,
Ulrich KrOerke, Manfred Kunz, Herman Mihran Somer

EDITORS Rolf Frobose, Johannes FOssel

CHIEF EDITOR Johannes FOssel

System Number 60

Springer-Verlag Berlin Heidelberg GmbH 1987

 LITERATURE CLOSING DATE: 1986
IN SOME CASES MORE RECENT DATA HAVE BEEN CONSIDERED

Library of Congress Catalog Card Number: Agr 25-1383

ISBN 978-3-662-11383-7 ISBN 978-3-662-11381-3 (eBook)

DOl 10.1007/978-3-662-11381-3

This work is subject to copyright. All rights are reserved, whether the whole or part of the material Is concerned, specifically
those of translation, reprinting, reuse of illustrations, broadcasting, reproduction by photocopying machine or similar means,
and storage in dats banks. Under § 54 of the German Copyright Law where copies are made lor other than private use, a
lee is payable to "Verwertungsgesellschalt Wort", Munich.

©by Springer-Verlag Be~in Heidelberg 1987

Originally published by Springer-Ve~ag Berlin Heidelberg New York Tokyo in 1987
Soltcover reprint of the hardcover 8th edition 1987

The use of registered names, trademarks, etc., in this publication does not imply, even in the absence of a specific statement,
that such names are exempt from the relevant protective laws and regulations and therefore free lor general use.
 Preface

The present volume finalizes the coverage of organocopper compounds. A complete

formula and ligand index for the Gmelin organocopper series will appear shortly as" Organa-
copper Compounds" 5.
The volume describes mononuclear compounds with ligands bonded by two or more
carbon atoms as well as all di- to octanuclear and polymeric compounds. Mononuclear
compounds with ligands bonded by one carbon atom have already been described in Vol-
umes 1 (published in 1985), 2 (published in 1983), and 3 (published in 1986).
As structural elucidation in organocopper chemistry gained more attention only in the
last few years, the terms "mononuclear", "dinuclear" etc. have been used as explained
in "Organocopper Compounds" 1, 1985, pp. 3/4: all compounds are treated with their small-
est formula unit unless a higher nuclearity has been proved. As a consequence, most
of the species treated in volumes 1 to 3 are described there because of insufficient structural
information although they are alleged not to be monomeric. This way, many of the better
characterized compounds appear in the present volume which is reflected by the more
than eighty X-ray structure figures. Generally, nuclearity and structure are not only deter-
mined by the coordination properties of the ligands, but also by steric requirements, and
may therefore widely differ for analogous compounds.
For abbreviations and dimensions used throughout this volume, see p. X.

Frankfurt am Main, July 1987 Johannes Fussel

Remarks on Abbreviations and Dimensions
Most compounds and reagents in this volume are presented in tables. Unless otherwise
stated, they are arranged in the tables according to the numbers of C atoms in the empirical
formula. For the sake of conciseness, some abbreviations are used and some dimensions
are omitted in the tables. This necessitates the following clarification.
Geometric Isomers are designated according to the IUPAC rules. Structural labels are
missing when authors fail to report structural details.
Temperatures are given in OC, otherwise K stands for Kelvin. Abbreviations used with
temperatures are m. p. for melting point, b. p. for boiling point, and dec. for decomposition.
Nuclear magnetic resonance is abbreviated as NMR, noise decoupling is indicated by
braces {}.Chemical shifts are given as I) values in ppm with the positive sign for downfield
shifts. Reference substances are Si (CH 3) 4 for 1H and 13C NMR, CFCl3 for 19F NMR, and H3 P04
for 31 P NMR.
Multiplicities of the signals are abbreviated as s, d, t, q (singlet to quartet), quint, sext,
sept (quintet to septet), and m (multiplet); terms like dd (double doublet) and t's (triplets)
are also used. Assignments referring to labeled structural formulas are given in the form
C-4, H-3, 5. Coupling constants "J in Hz are given as J(A, B) or as J(1, 3) referring to
labeled structural formulas, n is the number of bonds between the coupled nuclei.
Optical spectra are labeled as IR (infrared), Raman, and UV (electronic spectrum includ-
ing the visible region). IR bands and Raman lines are given in cm- 1, the assigned bands
are usually labeled with the symbols v for stretching vibration and I) for deformation vibration.
Intensities are indicated by the common qualitative terms (vs, s, m, w, vw) or as numerical
relative intensities in parentheses. Multiplicities are abbreviated as with NMR. The UV ab-
sorption maxima, A.max• are given in nm followed by the extinction coefficient e(L · cm- 1 •
mol- 1) or logE in parentheses; sh means shoulder, br means broad. If reported, solvents
or the physical state are given in parentheses immediately after the spectral symbol.
Electron paramagnetic resonance and electron spin resonance are abbreviated as EPA
and ESR, hyperfine coupling constants are given as a(X).

Further abbreviations:
de calculated density
dm experimental density
[M]+ molecular ion in mass spectroscopy
aq. aqueous
cone. concentrated
emf electromotive force
NQR nuclear quadrupole resonance
SCE saturated calomel electrode
soln. solution
THF tetrahydrofuran
i-C3 H7 isopropyl CH (CH 3 ) 2
s-C4 H9 sec-butyl CH (CH 3)C2 H5
t-C4 H9 tert-butyl C (CH 3 )a
 XI

Table of Contents

Page
1.2 Compounds with Ligands Bonded by Two C Atoms 1
1.2.1 Copper(ll) Acetylide CuC 2 . . . . 1
1.2.2 Complexes with Alkenes . . . . . . . 2
Copper(O) Complexes of the Type 2LCu 2
Cations of the Type [2LCu]+ in the Gas Phase 3
Compounds of the Type 2LCuX or [2LCu]X with 2L=Acyclic Alkene 4
Compounds of the Type 2LCuX or [ 2LCu]X with 2L=Semicyclic or Cyclic Alkene 19
Anions of the Types [ 2LCuCl2]- and [2LCuCl 3]2- 24
Compounds of the Type 2LCuDmX or [2LCuDmlX . . . . . . . . . . 25
Diketonato Complexes of the Type 2LCu(RCOCHCOR')n . . . . . . . 33
Trispyrazol-1-ylborate Complexes of the Types 2LCu(C3 HR 2N2)BH and
2LCu(C 3 H3 N2)3 BHCuX . . . . . . . 34
Reagents of the Type 2LCuR 2Li . . . . 36
Complexes with Two Alkene Ligands . 36
Complexes with Three Alkene Ligands 39
1.2.3 Complexes with Alkynes 40
Copper(O) Complexes with C2H2 40
Binary Copper(l) Complexes with C2H2 42
Ternary Copper(l) Complexes with C2H2 and NH 4Cl 47
Other Ternary Copper(l) Complexes with C2H2 50
Copper(ll) Complexes with C2H2 . . . . . . 53
Complexes with Other Alkynes . . . . . . . 54
1.2.4 Compounds with Dicarbaborane Ligands 57
Compounds with 7,8-Dicarba-nido-undecaborane Ligands 59
Compounds with 1,2-Dicarba-closo-dodecaborane Ligands 62
Compounds with Bisdicarbaborane Ligands . . . . . . . 62
1.2.5 Compounds with o-Bonded Ligands and Cupracyclic Compounds 63

1.3 Compounds with Ligands Bonded by Three C Atoms 65

1.4 Compounds with Ligands Bonded by Four C Atoms 66
1.5 Compounds with Ligands Bonded by Five C Atoms 69
1.6 Compounds with Diene, Triene, Tetraene, Enyne, or Dlyne Ligands 83
1.6.1 Reagents of the Type cyclo-C 8 H12CuR 2MgBr . . . . . . . . . . 83
1.6.2 Other Compounds with One Diene, Triene, Tetraene, Enyne, or Diyne Ligand 84
1.6.3 Compounds with Two Diene Ligands 97
1.7 Compounds with Arene Ligands 100

2 Binuclear Compounds . . . . . 102

2.1 Compounds with Alkyl, Alkenyl, Alkynyl, and Aryl Groups 102
2.1.1 Compounds of the Type (RCub 102
2.1.2 Lithium Organocuprates . . 103
2.1.3 Magnesium Organocuprates 106
2.1.4 Other Compounds 108

2.2 Carbonyl& 110

2.3 Isocyanide Compounds 123

XII

Page

2.4 Copper(!) Ketenlde Cu 2C20 and Its Complexes 127

2.5 Compounds of the Type Cu(f.1- 2L)Cu with a-Bonded 2L Ligands 128
2.5.1 Compounds with 2L=Alkylene, Arylene, or Heterocyclic Bridges 128
2.5.2 Dicupriodicarba-closo-dodecaboranes . . 135
2.5.3 Copper(l) Acetylide Cu 2C2 and Its Hydrates 136
2.5.4 Complexes of Cu 2C2 . . . . . . . . 150
2.5.5 Compounds of the Type CuC:CZC:CCu . . 152
2.5.6 Complexes of CuC:CZC:CCu . . . . . . 161
2.6 Cyclic Copper Yllde Complexes of the Type Cu(f.1-CH 2 MR 1R2CH 2) 2Cu 162
2.7 1t Complexes with Alkenes or Alkynes . . . . . 165
2.7.1 Compounds with One Alkene or Alkyne Ligand 165
2.7.2 Compounds with Two Alkene or Alkyne Ligands 168
2.7.3 Compounds with More than Two Alkene or Alkyne Ligands 172
2.8 Other 1t Complexes 173

3 Trlnuclear Compounds 192

4 Tetranuclear Compounds 197

4.1 Compounds of the Type (RCu) 4 197
4.2 Compounds of the Type R5Cu 4LI 213
4.3 Compounds of the Type R6Cu 4 Mg 213
4.4 Compounds of the Type R4Cu 4 M 2X2 214
4.5 Carbonyls 216
4.6 Compounds of the Types (RC:C) 8Cu 4 M2(P(C 6H5hR'h and
(RC:C) 8Cu 41r2Fe 2(CO)a(P(C 6H5) 3h 217
4.7 1t Complexes of the Type LnCu 4X4 220
4.8 1t Complexes of the Type 2 LCu 4 D2 X4 225
4.9 Other Compounds . . . 229

5 Pentanuclear Compounds 240

6 Hexanuclear Compounds 243

7 Octanuclear Compounds 250

8 Polynuclear Compounds 253

Table of Conversion Factors 271