A two-coordinate boron cation featuring

CB
1
C bonding
Yoshiaki Shoji
1
*
, Naoki Tanaka
1
, Koichiro Mikami
2
, Masanobu Uchiyama
2,3
and Takanori Fukushima
1
Two-coordinate boron cations (R
2
B
1
), referred to as borinium ions, are chemical species in which the boron bears only four
valence electrons, and that are isoelectronic with hypothetical carbon dications (R
2
C
21
). Although lone-pair-donating
substituents such as amino groups have enabled the isolation of several borinium ions, diarylated and dialkylated borinium
derivatives remain entirely unexplored. Here, we present the synthesis, structure and reactivity of the dimesitylborinium
ion, which displays unexpectedly high thermal stability. X-ray crystallography and
11
B NMR spectroscopy, supported by
density functional theory calculations, reveal that the borinium ion adopts a linear two-coordinate structure in both the
solid state and in solution. The boron centre is stabilized by p
p
bonding from the mesityl groups and is free from
coordination by the counterion or solvent molecules. This diarylborinium ion possesses exceptional Lewis acidity, accepting
a pair of electrons from CO
2
to cause an unusual deoxygenation reaction.
T
he octet rule is a fundamental principle of chemistry, describ-
ing how main group atoms tend to combine so as to have eight
electrons in their valence shell. It applies most rigorously to
main group elements of the second period. Boron, the third
element in the second period, accumulates only six valence electrons
in its neutral three-coordinate state (borane), R
3
B (I, Fig. 1a) and it
is therefore favourable for it to accept an electron pair into its vacant
2p orbital to full an octet. This strong Lewis acidity (as well as
borons low electronegativity) gives boron compounds a unique
chemistry that plays a vital role in a wide range of elds, including
organic transformations
1,2
, supramolecular complexation
35
and
chemical bonding theory
614
.
So, what would happen if borane were to lose one further chemi-
cal bond? In this context, two-coordinate cationic boron species
with only four valence electrons, referred to as borinium ions
(parent H
2
B

and II, Fig. 1a), are fascinating because they

deviate signicantly from the octet rule and may show unprece-
dented reactivity arising from their extraordinary Lewis acidity. It
is also interesting to note that the borinium ion is isoelectronic
with the hypothetical two-coordinate carbon dication
(III, Fig. 1a). In addition to extensive studies of three- and four-
coordinate boron cations
1518
, several efforts have been devoted to
creating two-coordinate borinium ions
15,16,1926
. For instance,
electron ionization of a variety of gas-phase boranes (R
3
B; R H,
Me, F, Cl, and so on) under high-vacuum conditions was
found to generate borinium ions (R
2
B

) that can be detected by

mass spectrometry
19,20
.
The rst attempt to synthesize a borinium ion in solution dates
back to 1958, where the reaction of chlorodiphenylborane
(Ph
2
BCl) with AlCl
3
in nitrobenzene or methyl ethyl ketone was
reported to afford a mixture containing the diphenylborinium
ion (Ph
2
B

) (ref. 21). However, later re-examination revealed

that, rather than borinium ion formation, this reaction yields
three- and/or four-coordinate boron cations bonded to solvent
molecules
22,23
. In 1982, Noth and co-workers demonstrated the
rst successful isolation of a two-coordinate boron cation by
using dimethylamino and 2,2,6,6-tetramethylpiperidino groups
as substituents (IV, Fig. 1b)
24
. Monoarylated and monoalkylated
derivatives containing only one stabilizing amino group (V and
VI, Fig. 1b) were reportedly hard to isolate because of their chemi-
cal instability. Thus, a general consensus has developed that the
synthesis of a two-coordinate boron cation requires lone-pair-
donating substituents, such as amino groups, which can compen-
sate for the electron deciency on boron through dative p-
bonding from heteroatoms
15,16,25,26
. The chemistry of borinium
ions that are devoid of such lone pair donation has
remained unexplored.
Here, we report the isolation and full structural characterization
of a diarylborinium ion (Mes
2
B

; Mes (mesityl) 2,4,6-trimethyl-

phenyl, Fig. 1c). We further demonstrate the extraordinary reactivity
of this borinium ion through a peculiar CO
2
activation reaction. Key
to the present achievement is the use of chemically inert and weakly
nucleophilic counterions such as undecachloro carborane
([HCB
11
Cl
11
]
2
) (refs 27, 28) and tetrakis(pentauorophenyl)borate
([(C
6
F
5
)
4
B]
2
). Another part of the synthetic strategy is the use of
mesityl groups that offer steric bulk around the boron centre and
the possibility of p
p
electronic stabilization. Mesityl substituents
were used for the synthesis of the rst silylium ion (Mes
3
Si

) (ref. 29),
where related steric and electronic constraints were necessary for
stabilization. We found that Mes
2
B

salts of [HCB
11
Cl
11
]
2
(1a)
and [(C
6
F
5
)
4
B]
2
(1b) (Fig. 1c) possess high thermodynamic
stability in both the solid state and in solution and can therefore
be readily obtained on a large synthetic scale.
Results and discussion
For the synthesis of 1a, dimesityluoroborane (Mes
2
BF) was reacted
with 1 equiv. triethylsilylium carborane (Et
3
Si[HCB
11
Cl
11
]) (ref. 27)
in o-dichlorobenzene (ODCB) at 25 8C for 5 min. When hexane
vapour was allowed to diffuse into the resulting mixture, 1a
formed as a colourless crystalline material (86% yield). Although
compound 1a decomposes immediately upon exposure to air, it
exhibits surprisingly high thermal stability under an inert
1
Chemical Resources Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan,
2
Graduate School of
Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan,
3
Advanced Elements Chemistry Research Team,
RIKEN Centre for Sustainable Resource Science (CSRS) and Elements Chemistry Laboratory, RIKEN, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan.
*e-mail: yshoji@res.titech.ac.jp
ARTICLES
PUBLISHED ONLINE: 11 MAY 2014 | DOI: 10.1038/NCHEM.1948
NATURE CHEMISTRY | ADVANCE ONLINE PUBLICATION | www.nature.com/naturechemistry 1
2014 Macmillan Publishers Limited. All rights reserved.

atmosphere, not showing decomposition until heated to 320 8C
(Supplementary Fig. 3). Left standing under argon at ambient
temperature, 1a showed no sign of decomposition after 1 year.
The
11
B NMR spectrum (128.0 MHz) of 1a at 25 8C in deuter-
ated ODCB (ODCB-d
4
) shows a very broad signal from the
Mes
2
B

cation at d 93.3 ppm with a half-width (W

1/2
) of
5,000 Hz, as well as three signals due to the carborane anion at
d 22.4, 210.1 and 213.2 ppm (Supplementary Fig. 1).
Importantly, the
11
B NMR signal of Mes
2
B

is signicantly
further downeld than those reported for other two-coordinate
boron cations (in the range 22.659.6 ppm)
17,18
, indicating excep-
tional electron deciency at the boron centre. Taking this downeld
shift into account, coordination of the counter-anion or solvent
molecules to the cation centre seems unlikely. The
13
C NMR
signals due to the aromatic carbons of 1a appear at 155.2 (C
ortho
),
158.9 (C
para
) and 119.2 ppm (C
meta
) (Supplementary Fig. 20). The
former two signals are signicantly deshielded compared to the
corresponding carbons of trimesitylborane (140.3 and 138.9 ppm
for C
ortho
and C
para
, respectively, Supplementary Fig. 21), suggesting
a certain degree of p donation from the Mes groups to the boron
centre in 1a.
X-ray structural analysis (see Supplementary Information) of 1a
(Fig. 2a and Supplementary Fig. 3) reveals well-separated cations
and anions. The shortest distance between the boron atom of
R
B
R
R
I
III
B R
R
R
C R R
R C R
++
++
N N B
+
R N B
+
AlBr
4

AlBr
4

IV V (R = Ph), VI (R = Me)
B
+
[HCB
11
Cl
11
]

B
+
[(C
6
F
5
)
4
B]

Et
3
Si[HCB
11
Cl
11
]
ODCB, 25 C
ODCB, 25 C
[Et
3
Si(mesitylene)]
+
[(C
6
F
5
)
4
B]

Mes
2
BF
1a
1b
R B R
+
II
B R R
+
a
b
c
Figure 1 | Schematic representations of chemical compounds. a, Structures of a planar three-coordinate borane (I), a linear two-coordinate borinium ion (II)
and a hypothetical two-coordinate carbon dication (III). Their Lewis structures are shown in parentheses. Borinium ions II, consisting of sp-hybridized boron,
are characterized by the presence of two vacant 2p orbitals on a central boron atom. b, Typical examples of reported two-coordinate boron cations (IVVI),
whose vacant 2p orbitals of boron are lled by dative p bonds with amino groups. c, Synthesis of Mes
2
B

salts of [HCB
11
Cl
11
]
2
(1a) and [(C
6
F
5
)
4
B]
2
(1b).
The two mesityl rings of Mes
2
B

are not coplanar to one another, as a consequence of steric effects and p

p
bonding with the boron atom. Mes 2,4,6-
trimethylphenyl; ODCB o-dichlorobenzene.
b a
B1
C1
C2
C3
C4
C5
C6
C10
C11
C12
C13
C14
C15
B1 C1
C2 C3
C4
C2* C3*
Figure 2 | Crystal structures of 1a and 1b (50% probability ellipsoids). a,b, Molecular structures of 1a (a) and 1b (b). Hydrogen atoms are not shown.
Boron, carbon, uorine and chlorine atoms are in magenta, grey, yellow-green and green, respectively. For 1b, a quarter of the whole structure constitutes
the asymmetric unit; numbers with an asterisk are related by symmetry. Selected bond lengths () and angles (deg) for 1a: C1B1 1.459(3), C1C2
1.429(3), C1C6 1.422(3), C2C3 1.382(3), C3C4 1.398(3), C4C5 1.391(3), C5C6 1.384(3), C10B1 1.458(3), C10C11 1.428(3), C10C15
1.431(3), C11C12 1.375(3), C12C13 1.395(3), C13C141.396(3), C14C15 1.374(3), C1B1C10172.1(2), dihedral angle (deg) between the mean
planes of the two aromatic rings 80.67(9). Selected bond lengths () for 1b: C1B1 1.4568(18), C1C2 1.420(2), C2C3 1.378(3), C3C4 1.392(2).
In both 1a and 1b, the short C
ipso
B bond and the quinoidal character in the mesityl groups of Mes
2
B

reect the delocalization of positive charge through

p
p
bonding.
ARTICLES
NATURE CHEMISTRY DOI: 10.1038/NCHEM.1948
NATURE CHEMISTRY | ADVANCE ONLINE PUBLICATION | www.nature.com/naturechemistry 2
2014 Macmillan Publishers Limited. All rights reserved.

Mes
2
B

and a chlorine atom of the carborane anion (4.562(2) )

is much longer than the sum of the van der Waals radii (3.67 )
(ref. 30). The geometry at boron in the cation is close to linear
(/C
ipso
BC
ipso
172.1(2)8), as expected for sp-hybridization.
The dihedral angle between the two mesityl groups is 80.67(9)8, a
consequence of steric effects. The C
ipso
B bond lengths (1.459(3)
and 1.458(3) ) are shorter than typical CB single bond lengths
(1.59 ) (ref. 31), reecting the overall positive charge and some
degree of p
p
bonding. This is conrmed by the quinoidal character
in the mesityl groups, where the mean length of the C
ipso
C
ortho
bonds (1.428(3) ) is longer than those of the other CC bonds
in the aromatic ring (1.379(3) and 1.395(3) ).
For a better understanding of the structural features of Mes
2
B

we
performed density functional theory (DFT) calculations on a coun-
terion-free model of Mes
2
B

(a singlet state in vacuum) at the

M06-2X/6-31 G(d) level of theory (see Supplementary
Information). In the optimized structure (Fig. 3, Supplementary
Fig. 7), all the CB and CC bond lengths agree well with those
observed for the crystal structure of 1a (Fig. 2a). This is consistent
with well-separated cations and anions, as found experimentally.
The calculated dihedral angle between the two Mes groups (61.968)
is smaller than that observed experimentally (80.67(9)8), most prob-
ably due to the internal maximization of dispersion forces within the
isolated gas-phase cation relative to external dispersion forces arising
from cation/anion contacts in the crystal. The natural population
analysis charge distribution conrms that positive and negative
charges are located predominately on the boron (1.277) and C
ipso
(20.657) atoms, respectively (Supplementary Fig. 8). As expected,
the lowest unoccupied molecular orbital (LUMO) and LUMO1 of
Mes
2
B

(Fig. 3) involve the vacant 2p orbitals of boron, whilst the

highest occupied molecular orbital (HOMO) and HOMO1 are
localized solely on the Mes groups. The quinoidal character of the
boronmesityl substituents, suggested by X-ray crystallography, is
reected in the HOMO2 and HOMO3 orbitals (Fig. 3), which
demonstrate p donation from the arene rings to the boron centre.
Based on second-order perturbation analysis, secondary orbital inter-
actions (p bonding) between boron and the C
ipso
C
ortho
p bonds of
the Mes groups certainly operate, providing Mes
2
B

with substantial
stabilization energy (43.28 kcal mol
21
) (Supplementary Fig. 9). The
Wiberg bond index of the C
ipso
B bond (1.065) also indicates
partial p-bond character around the boron centre (Supplementary
Fig. 10). The gauge-independent atomic orbital calculation on the
counterion-free model of Mes
2
B

in vacuum (89.7 and 102.4 ppm

at the B3LYP/6-311G(3df,2pd) and M06-2X/6-
311G(3df,2pd) level of theory, respectively) virtually reproduces
the chemical shift of the boron centre of Mes
2
B

observed in
ODCB-d
4
(d 93.3 ppm). This result indicates that coordination of
the counter-anion or solvent molecules to the boron centre of 1a
is insignicant.
We initially supposed that the isolation of such a Lewis-acidic
species as Mes
2
B

would require a counterion having the particular

inertness of the [HCB
11
Cl
11
]
2
carborane anion, as it does in
silylium ion chemistry
27,29
. However, the more commonly available
tetraarylborate anion [(C
6
F
5
)
4
B]
2
is also applicable for the synthesis
of the borinium ion. In a manner similar to that for 1a, 1b was iso-
lated (92% yield) as a stable crystalline material (decomposition
temperature 192 8C, Supplementary Fig. 4) by the reaction of
Mes
2
BF and [Et
3
Si(mesitylene)]

[(C
6
F
5
)
4
B]
2
(ref. 32) in ODCB
at 25 8C (Fig. 1c). Single-crystal X-ray crystallography (Fig. 2b)
as well as
1
H,
11
B and
13
C NMR spectroscopy (Supplementary
Figs 22, 2 and 23, respectively) showed that the structural features
of the Mes
2
B

ion in 1b are essentially identical to those observed

for 1a. Thus, the boron centre of Mes
2
B

is not subject to coordi-

nation by the anion. We would like to emphasize that the use of
such a readily available anion such as [(C
6
F
5
)
4
B]
2
greatly enhances
the synthetic accessibility of the diarylborinium salt.
The Mes
2
B

ion has low-lying vacant orbitals (25.41 and

24.84 eV for LUMO and LUMO1, respectively, Fig. 3) on
the boron centre, which apparently does not accept signicant
electron density from the counterions or chloroarene solvent mol-
ecules. Although Mes
2
B

is certainly stabilized by p
p
bonding
from the mesityl groups, its behaviour may differ from that of
conventional diaminoborinium ions
15,16,24,25
, which demonstrate
lone pair donation to the boron centre. The DFT calculations
of (Me
2
N)
2
B

as a model compound at the M06-2X/6-31G(d)

level of theory revealed that the two molecular orbitals, consisting
of the vacant 2p orbitals on boron, lay at an energy level as high
as 23.73 eV (degenerated, Supplementary Figs 11 and 12).
The Mes
2
B

ion, featuring low-lying vacant orbitals, possesses

exceptional Lewis acidity and readily engages in a peculiar deoxy-
genation reaction of CO
2
. When an ODCB solution of 1a at 25 8C
was exposed to CO
2
gas at 1 bar pressure, colourless crystals
immediately began to form. X-ray crystallography revealed that
the resulting material is a salt of the MesC;O

aroyl cation with

[HCB
11
Cl
11
]
2
as counterion (2a, Supplementary Fig. 6). As with
other reported examples of aroyl cations
33
, crystalline 2a showed a
strong CO stretching vibration at 2,276 cm
21
in its infrared
spectrum. Similarly, 1b reacted with CO
2
to afford the MesC;O

salt of [(C
6
F
5
)
4
B]
2
(2b). The isolated yields of 2a (37%) and 2b
(33%) are comparable with one another. The reaction of Mes
2
B

and CO
2
should also produce oxoborane MesBO (ref. 34)
and its aggregates (boroxin and dioxadiboretane); however, these
could not be isolated because of the occurrence of side reactions
with unreacted Mes
2
B

, resulting in a complex mixture. We

considered that the observed arylationdeoxygenation is triggered
by the coordination of an oxygen atom of CO
2
to the boron
centre of Mes
2
B

, leading to polarization of CO
2
. Most probably,
E (eV)
LUMO+1 ( 4.84)
HOMO2 (11.81)
HOMO3 (12.29)
HOMO1 (11.70)
HOMO (11.66)
LUMO (5.41)
Figure 3 | DFTcalculation of Mes
2
B
1
at the M06-2X/6-311G(d) level.
Localized KohnSham orbitals of Mes
2
B

in its optimized geometry are

shown. Energy levels (eV) are given in parentheses. The low-lying LUMO
and LUMO1 of Mes
2
B

involve the vacant 2p orbitals of boron. The

HOMO2 and HOMO3 reect the quinoidal character of Mes
2
B

arising
from p
p
bonding between the mesityl groups and boron.
NATURE CHEMISTRY DOI: 10.1038/NCHEM.1948
ARTICLES
NATURE CHEMISTRY | ADVANCE ONLINE PUBLICATION | www.nature.com/naturechemistry 3
2014 Macmillan Publishers Limited. All rights reserved.

the resulting positively charged carbon atom in CO
2
then forms
a covalent bond with the negatively charged C
ipso
atom of
Mes
2
B

. This scenario was rationalized by DFT calculations using

articial force-induced reaction (AFIR) analysis based on an
M06-2X method.
As shown in Fig. 4, the oxygen atom of CO
2
approaches the
boron centre of Mes
2
B

to form CP1 with a small endothermicity

(4.4 kcal mol
21
). The C
ipso
B

C
ipso
angle (179.98 in RT) is
deformed by 37.38 and the CO bond length (1.16 in RT) is
elongated by 3%. CC bond formation in the four-membered
ring CP2 via TS1 requires a small activation energy
(4.2 kcal mol
21
). CP2 lies in an energy state 5.7 kcal mol
21
lower
than RT. The C
ipso
B bond dissociation in CP2 through TS2 occurs
with a small energy barrier (4.6 kcal mol
21
) to afford CP3, which
exothermically (1.6 kcal mol
21
) disproportionates into MesC;O

and oxoborane MesBO. This arylationdeoxygenation of CO

2
with a Lewis acid is unprecedented and provides a sharp contrast to
common reactions between CO
2
and nucleophiles.
In summary, we have synthesized and isolated a two-coordinate
boron cation with CB

C bonding. With its relatively easy

synthetic accessibility and unique oxophilicity, the diarylborinium
ion provides a platform for molecular Lewis-acid chemistry
and may offer a powerful tool for exploring new chemical
transformations
15,16,3538
.
O C O
B
+
RT
(0.0)
B
C
O
O
B
C
O
O
+
B
C O
O
B
C O
O
B
O C
O
C
+
CP1
(+4.4)
TS1
(+8.6)
CP2
(5.7)
TS2
(1.1)
CP3
(9.0)
PD
(10.6)
+
+
0.0
10.0
10.0
E (kcal mol
1
)
Oxoborane
Mes
2
B
O
MesC
+
O
B O
+
+
+
+
+
Figure 4 | Energy diagram of the arylationdeoxygenation of CO
2
with Mes
2
B
1
to form MesC;O
1
at the PCM(o-dichlorobenzene)-M06-2X/6-
3111G(d,p)//M06-2X/6-311G(d) level. Energy changes at the M06-2X/6-311G(d,p) level are shown in kcal mol
21
. RT, CP, TS and PD indicate reactant,
complex (intermediate), transition state and product, respectively. At the initial stage, the oxygen atom of CO
2
approaches the boron centre of Mes
2
B

to
give CP1. CC bond formation then occurs to form CP2 through TS1. The C
ipso
B bond dissociation in CP2 through TS2 occurs to form CP3, which nally
disproportionates into MesC;O

and oxoborane MesBO.

ARTICLES
NATURE CHEMISTRY DOI: 10.1038/NCHEM.1948
NATURE CHEMISTRY | ADVANCE ONLINE PUBLICATION | www.nature.com/naturechemistry 4
2014 Macmillan Publishers Limited. All rights reserved.

Methods
The handling of air- and/or moisture-sensitive compounds was performed either using
standard Schlenk-line techniques or in a glove box under argon. Anhydrous hexane was
dried by passage through an activated alumina column and a Q-5 column (Nikko
Hansen). ODCB and ODCB-d
4
were dried over CaH
2
and freshly distilled before use.
Mes
2
BF (ref. 39), Et
3
Si[HCB
11
Cl
11
] (ref. 27) and [Et
3
Si(mesitylene)]

[(C
6
F
5
)
4
B]
2
(ref. 32) were prepared according to reported procedures.
Synthesis of Mes
2
B
1
[HCB
11
Cl
11
]
2
(1a). To an ODCB solution (1.0 ml) of
Et
3
Si[HCB
11
Cl
11
] (59.0 mg, 9.26 10
22
mmol) was added Mes
2
BF (24.8 mg,
9.26 10
22
mmol), and the mixture was stirred at 25 8C for 5 min under argon.
The reaction mixture was partially evaporated under lowered pressure to reduce
the amount of solution to 0.5 ml. Hexane vapour was allowed to diffuse into the
resulting solution, affording a crystalline material, which was ltered off, washed
with hexane (3.0 ml) and dried under reduced pressure to give 1a as colourless
crystals (61.2 mg, 7.94 10
22
mmol) in 86% yield. Decomposition point (d.p.)
(in a sealed tube under Ar), 320 8C. Fourier transform infrared spectroscopy (FT-
IR) (attenuated total reectance (ATR)): n (cm
21
) 3,020, 2,962, 2,928, 2,852, 1,604,
1,585, 1,542, 1,450, 1,371, 1,288, 1,118, 1,009, 955, 898, 855, 754, 738, 713, 671.
1
H NMR (400 MHz, ODCB-d
4
): d (ppm) 6.74 (s, Ar-H, 4H), 2.98 (br, CH, 1H),
2.43 (s, CH
3
, 12H), 2.17 (s, CH
3
, 6H).
11
B NMR (128 MHz, ODCB-d
4
): d (ppm)
93.3 (W
1/2
5,000 Hz), 22.4, 210.1, 213.2.
13
C NMR (100 MHz, ODCB-d
4
):
d (ppm) 158.9 (C
para
), 155.2 (C
ortho
), 119.2 (C
meta
), 47.3 (CH), 23.2 (two signals,
CH
3
), one peak of the aromatic carbon, ipso position to the boron, was not
observed.
1
H,
13
C,
11
B NMR spectra of 1a are shown in Supplementary Figs 19, 20
and 1, respectively.
Synthesis of Mes
2
B
1
[(C
6
F
5
)
4
B]

(1b). Compound 1b was obtained as colourless

crystals (92% yield) from Mes
2
BF and [Et
3
Si(mesitylene)]

[(C
6
F
5
)
4
B]
2
in a
manner similar to that for 1a. d.p. (in a sealed tube under argon): 192 8C. FT-IR
(ATR): n (cm
21
) 2,958, 2,929, 2,867, 1,644, 1,606, 1,557, 1,514, 1,458, 1,409, 1,383,
1,372, 1,288, 1,271, 1,160, 1,084, 1,034, 975, 862, 770, 754, 683, 662.
1
H NMR
(400 MHz, ODCB-d
4
): d (ppm) 6.74 (s, Ar-H, 4H), 2.43 (s, CH
3
, 12H), 2.17
(s, CH
3
, 6H).
11
B NMR (128 MHz, ODCB-d
4
): d (ppm) 93.5 (W
1/2
4,400 Hz),
216.5.
13
C NMR (100 MHz, ODCB-d
4
): d (ppm) 159.0 (C
para
), 155.2 (C
ortho
),
148.5 (C
borate
; dm,
1
J
CF
241 Hz), 138.3 (C
borate
; dm,
1
J
CF
245 Hz), 136.4
(C
borate
; dm,
1
J
CF
245 Hz), 124.5 (C
borate
; br), 119.2 (C
meta
), 22.9 (CH
3
), 22.7
(CH
3
), one peak of the aromatic carbon, ipso position to the boron, was not
observed.
19
F NMR (376 MHz, ODCB-d
4
): d (ppm) 2132.8, 2163.4, 2167.2.
1
H,
13
C,
11
B,
19
F NMR spectra of 1b are shown in Supplementary Figs 22, 23, 2
and 24, respectively.
Synthesis of MesC;O
1
[HCB
11
Cl
11
]
2
(2a). An ODCB solution (3.0 ml) of 1a
(200 mg, 0.259 mmol) was degassed by freezepumpthaw cycles (three times) and
then exposed to CO
2
gas (1.0 l) at 25 8C under 1 bar pressure, whereupon
colourless crystals formed. After hexane vapour was allowed to diffuse into the
reaction mixture, the resulting crystals were ltered off, washed with hexane
(5.0 ml) and dried under reduced pressure to give 2a as colourless crystals
(64.4 mg, 9.63 10
22
mmol) in 37% yield. d.p. (in a sealed tube under Ar):
344 8C. FT-IR (ATR): n (cm
21
) 3,031, 2,964, 2,832, 2,859, 2,175, 1,598, 1,539,
1,504, 1,463, 1,379, 1,345, 1,327, 1,300, 1,227, 1,213, 1,120, 1,010, 955, 903, 863,
740, 715, 671.
1
H NMR (400 MHz, ODCB-d
4
): d (ppm) 6.82 (s, Ar-H, 2H), 3.02
(br, CH, 1H), 2.32 (s, CH
3
, 6H), 2.20 (s, CH
3
, 3H).
11
B NMR (128 MHz, ODCB-
d
4
): d (ppm) 22.4, 210.0, 213.1.
13
C NMR (100 MHz, ODCB-d
4
): d (ppm) 165.0
(C;O), 160.7 (C
para
), 155.2 (C
ortho
), 132.2 (C
meta
), 84.7 (C
ipso
), 47.6 (CH), 24.3
(CH
3
), 21.5 (CH
3
).
1
H,
13
C,
11
B NMR spectra of 2a are shown in Supplementary
Figs 25, 26 and 27, respectively.
Synthesis of MesC;O
1
[(C
6
F
5
)
4
B]

(2b). Compound 2b was obtained as colourless

crystals (33% yield) from 1b in a manner similar to that for 2a. d.p. (in a sealed tube
under Ar): 197 8C. FT-IR (ATR): n (cm
21
) 2,958, 2,926, 2,876, 2,852, 2,190, 1,644,
1,597, 1,514, 1,459, 1,411, 1,384, 1,367, 1,301, 1,276, 1,217, 1,146, 1,085, 1,032, 975,
925, 906, 863, 773, 756, 727, 700, 684, 661.
1
H NMR (400 MHz, ODCB-d
4
): d (ppm)
6.83 (s, Ar-H, 2H), 2.32 (s, 6H), 2.21 (s, 3H).
11
B NMR (128 MHz, ODCB-d
4
):
d (ppm) 216.6.
13
C NMR (100 MHz, ODCB-d
4
): d (ppm) 164.9 (C ;O), 160.3
(C
para
), 154.9 (C
ortho
), 148.5 (C
borate
; dm,
1
J
CF
242 Hz), 138.3 (C
borate
; dm,
1
J
CF
242 Hz), 136.5 (C
borate
; dm,
1
J
CF
245 Hz), 124.2 (C
borate
; br), 84.1 (C
ipso
),
23.7 (CH
3
), 20.7 (CH
3
).
19
F NMR (376 MHz, ODCB-d
4
): d (ppm) 2132.7, 2162.9,
2166.8.
1
H,
13
C,
11
B,
19
F NMR spectra of 2b are shown in Supplementary Figs 28,
29, 30 and 31, respectively.
Crystallographic data deposition. Crystal data of 1a, 1b and 2a are available from
the Cambridge Crystallographic Data Centre under reference numbers CCDC-
978055, 978056 and 978057 (www.ccdc.cam.ac.uk/data_request/cif ).
Received 22 January 2014; accepted 7 April 2014;
published online 11 May 2014
References
1. Suzuki, A. Cross-coupling reactions of organoboranes: an easy way to construct
CC bonds (Nobel Lecture). Angew. Chem. Int. Ed. 50, 67236737 (2011).
2. Brown, H. C. Hydroboration (W. A. Benjamin, 1962).
3. Shinkai, S. & Takeuchi, M. Molecular design of synthetic receptors with
dynamic, imprinting, and allosteric functions. Bull. Chem. Soc. Jpn 78,
4051 (2005).
4. Mastalerz, M. The next generation of shape-persistent zeolite analogues:
covalent organic frameworks. Angew. Chem. Int. Ed. 47, 445447 (2008).
5. Wade, C. R., Broomsgrove, A. E. J., Aldridge, S. & Gabba , F. P. Fluoride ion
complexation and sensing using organoboron compounds. Chem. Rev.
110, 39583984 (2010).
6. Lipscomb, W. N. Boron Hydrides (W. A. Benjamin, 1963).
7. Moezzi, A., Olmstead, M. M. & Power, P. P. Boronboron double bonding in the
species [B
2
R
4
]
2
: synthesis and structure of [{(Et
2
O)Li}
2
{Mes
2
BB(Mes)Ph}], a
diborane(4) dianion analog of a substituted ethylene. J. Am. Chem. Soc.
114, 27152717 (1992).
8. Segawa, S., Yamashita, M. & Nozaki, K. Boryllithium: isolation, characterization,
and reactivity as a boryl anion. Science 314, 113115 (2006).
9. Wang, Y. et al. A stable neutral diborene containing a BB double bond. J. Am.
Chem. Soc. 129, 1241212413 (2007).
10. Shoji, Y. et al. A stable doubly hydrogen-bridged buttery-shaped diborane(4)
compound. J. Am. Chem. Soc. 132, 82588260 (2010).
11. Kinjo, R., Donnadieu, B., Celik, M. A., Frenking, G. & Bertrand, G. Synthesis and
characterization of a neutral tricoordinate organoboron isoelectronic with
amines. Science 333, 610613 (2011).
12. Braunschweig, H. et al. Ambient-temperature isolation of a compound with a
boronboron triple bond. Science 336, 14201422 (2012).
13. Hubner, A. et al. Conrmation of an early postulate: BCB two-electronthree-
center bonding in organo(hydro)boranes. Angew. Chem. Int. Ed. 51,
1251412518 (2012).
14. Braunschweig, H., Damme, A., Dewhurst, R. D. & Vargas, A. Bond-
strengthening p backdonation in a transition-metal p-diborene complex. Nature
Chem. 5, 115121 (2013).
15. Kolle, P. & Noth, H. The chemistry of borinium and borenium ions. Chem. Rev.
85, 399418 (1985).
16. Piers, W. E., Bourke, S. C. & Conroy, K. D. Borinium, borenium, and boronium
ions: synthesis, reactivity, and applications. Angew. Chem. Int. Ed. 44,
50165036 (2005).
17. Chiu, C-W. & Gabba , F. P. Diarylborenium cations: synthesis, structure, and
electrochemistry. Organometallics 27, 16571659 (2008).
18. Matsumoto, T. & Gabba , F. P. A borenium cation stabilized by an N-heterocyclic
carbene ligand. Organometallics 28, 42524253 (2009).
19. Osberghaus, O. Die isotopenhaiugkeit des bors. Massenspektrometrische
untersuchung der elektronenstoprodukte von BF
3
und BCI
3
. Z. Phys.
128, 366377 (1950).
20. Law, R. W. & Margrave, J. L. Mass spectrometer appearance potentials for
positive ion fragments from BF
3
, B(CH
3
)
3
, B(C
2
H
5
)
3
, B(OCH
3
)
3
, and
HB(OCH
3
)
2
. J. Chem. Phys. 25, 10861087 (1956).
21. Davidson, J. M. & French, C. M. The existence of an organic cation containing
boron. J. Chem. Soc. 114117 (1958).
22. Moodie, R. B., Ellul, B. & Connor, T. M. Evidence for the structure of boronium
ions from proton magnetic resonance and conductivity measurements. Chem.
Ind. 767768 (1966).
23. Uddin, M. K., Fujiyama, R., Kiyooka, S., Fujio, M. & Tsuno, Y. Preparation
and characterization of diphenylboron cation in solution. Tetrahedron Lett.
45, 39133916 (2004).
24. Noth, H., Staudigl, R. & Wagner, H-U. Contributions to the chemistry
of boron. 121. Dicoordinate amidoboron cations. Inorg. Chem. 21, 706716
(1982).
25. Higashi, J., Eastman, A. D. & Parry, R. W. Synthesis and characterization of salts
of the bis(diisopropylamido)boron(III) cation and attempted reactions to make
the corresponding bis(dimethylamido)boron(III) cation. Inorg. Chem. 21,
716720 (1982).
26. Courtenay, S., Mutus, J. Y., Schurko, R. W. & Stephan, D. W. The extended
borinium cation: [(tBu
3
PN)
2
B]

. Angew. Chem. Int. Ed. 41, 498501 (2002).

27. Reed, C. A. H

, CH
3

, and R
3
Si

carborane reagents: when triates fail.

Acc. Chem. Res. 43, 121128 (2010).
28. Korbe, S., Schreiber, P. J. & Michl, J. Chemistry of the carba-closo-
dodecaborate() anion, CB
11
H
12
2
. Chem. Rev. 106, 52085249 (2006).
29. Kim, K-C. et al. Crystallographic evidence for a free silylium ion. Science
297, 825827 (2002).
30. Mantina, M., Chamberlin, A. C., Valero, R., Cramer, C. J. & Truhlar, D. G.
Consistent van der Waals radii for the whole main group. J. Phys. Chem. A
113, 58065812 (2009).
31. Olmstead, M. M., Power, P. P., Weese, K. J. & Doedens, R. J. Isolation and X-ray
crystal structure of the boron methylidenide ion [Mes
2
BCH
2
]
2
(Mes2,4,6-
Me
3
C
6
H
2
): a boroncarbon double bonded alkene analog. J. Am. Chem. Soc.
109, 25412542 (1987).
NATURE CHEMISTRY DOI: 10.1038/NCHEM.1948
ARTICLES
NATURE CHEMISTRY | ADVANCE ONLINE PUBLICATION | www.nature.com/naturechemistry 5
2014 Macmillan Publishers Limited. All rights reserved.

32. Lambert, J. B., Zhang, S., Stern, C. L. & Huffman, J. C. Crystal structure of a
silyl cation with no coordination to anion and distant coordination to solvent.
Science 260, 19171918 (1993).
33. Davlieva, M. G., Lindeman, S. V., Neretin, I. S. & Kochi, J. K. Structural effects of
carbon monoxide coordination to carbon centres. p and s bindings in aliphatic
acyl versus aromatic aroyl cations. New J. Chem. 28, 15681574 (2004).
34. Pachaly, B. & West, R. Synthesis of a 1,3-dioxa-2,4-diboretane, an oxoborane
precursor. J. Am. Chem. Soc. 107, 29872988 (1985).
35. De Vries, T. S., Prokofjevs, A. & Vedejs, E. Cationic tricoordinate boron
intermediates: borenium chemistry from the organic perspective. Chem. Rev.
112, 42464282 (2012).
36. Braunschweig, H. et al. Controlled homocatenation of boron on a transition
metal. Nature Chem. 5, 563567 (2013).
37. Braunschweig, H. et al. Metal-free binding and coupling of carbon monoxide at a
boronboron triple bond. Nature Chem. 5, 10251028 (2013).
38. Litters, S., Kaifer, E., Enders, M. & Himmel, H-J. A boronboron coupling
reaction between two ethyl cation analogues. Nature Chem. 5, 10291034 (2013).
39. Eisch, J. J., Shai, B., Odom, J. D. & Rheingold, A. L. Aromatic stabilization of the
triarylborirene ring system by tricoordinate boron and facile ring opening with
tetracoordinate boron. J. Am. Chem. Soc. 112, 18471853 (1990).
Acknowledgements
This work was supported by KAKENHI (22750046). The authors thank C.A. Reed for his
instruction regarding carboranes synthesis and valuable discussions. RIKEN Integrated
Cluster of Clusters (RICC) provided the computer resources for the DFT calculations.
Author contributions
Y.S. and T.F. conceived and designed the work. Y.S. and N.T. performed the experiments.
Y.S., N.T. and T.F. analysed the experimental data. K.M. and M.U. performed the DFT
calculations and analysed the computational data. Y.S., M.U. and T.F. co-wrote the paper.
Additional information
Supplementary information and chemical compound information are available in the
online version of the paper. Reprints and permissions information is available online at
www.nature.com/reprints. Correspondence and requests for materials should be
addressed to Y.S.
Competing nancial interests
The authors declare no competing nancial interests.
ARTICLES
NATURE CHEMISTRY DOI: 10.1038/NCHEM.1948
NATURE CHEMISTRY | ADVANCE ONLINE PUBLICATION | www.nature.com/naturechemistry 6
2014 Macmillan Publishers Limited. All rights reserved.