Synthesis of cobalt and nickel 6,6′-diphenylbis(dicarbollides)

Article abstract of DOI:10.1007/s11172-019-2547-7

6,6′-Diphenyl derivatives of cobalt and nickel bis(dicarbollide) were synthesized starting from nido-carborane by the insertion—deboronation—insertion sequence of reactions. The by-products of the insertion of PhBCl₂ into the nido-carborane cage, diethyloxonium derivatives of nido-carborane [9-Et₂O-7,8-C₂B₉H₁₁] and [10-Et₂O-7,8-C₂B₉H₁₁], were isolated and characterized. Treatment of the latter with pyridine resulted in the elimination of one ethyl group to give the corresponding ethoxy derivatives. The structures of nido-carborane 10-diethyloxonium derivative and cobalt bis(dicarbollide) 6,6′-diphenyl derivative were established by X-ray diffraction analysis.

Full text of DOI:10.1007/s11172-019-2547-7

Russian Chemical Bulletin, International Edition, Vol. 68, No. 6, pp. 1239—1247, June, 2019
1239
Synthesis of cobalt and nickel 6,6´-diphenylbis(dicarbollides)*
A. V. Shmal´ko,а S. A. Anufriev,а A. A. Anisimov,а,b M. Yu. Stogniy,а I. B. Sivaev,а,c and V. I. Bregadze
аA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
28 ul. Vavilova, 119991 Moscow, Russian Federation.
E-mail: sivaev@ineos.ac.ru
bMendeleev University of Chemical Technology of Russia,
9 Miusskaya pl., 125047 Moscow, Russian Federation
cG. V. Plekhanov Russian University of Economics,
36 Stremyanny per, 117997 Moscow, Russian Federation
6,6´-Diphenyl derivatives of cobalt and nickel bis(dicarbollide) were synthesized starting
from nido-carborane by the insertion—deboronation—insertion sequence of reactions. The
by-products of the insertion of PhBCl2 into the nido-carborane cage, diethyloxonium derivatives
of nido-carborane [9-Et2O-7,8-C2B9H11] and [10-Et2O-7,8-C2B9H11], were isolated and char-
acterized. Treatment of the latter with pyridine resulted in the elimination of one ethyl group
to give the corresponding ethoxy derivatives. The structures of nido-carborane 10-diethyloxo-
nium derivative and cobalt bis(dicarbollide) 6,6´-diphenyl derivative were established by X-ray
diffraction analysis.
Key words: carboranes, metallacarboranes, phenyl derivatives.
The rapid development of the carborane chemistry in
the 1960s in many ways was ahead of the development and
introduction into everyday practice of modern instrumen-
tal methods of physicochemical analysis, first of all, nuclear
magnetic resonance spectroscopy. According to the R. N.
Grimes monograph,1 only synthesis was described for the
majority of carborane derivatives obtained in 1960—1970,
with any of physicochemical characteristics being absent.
Moreover, this problem is also present for many com-
pounds synthesized later.2 It was found that, in the absence
of reliable methods for product identification and control
of purity, synthetic procedures described in the literature
in some cases can lead to the formation of mixtures of
derivatives with a low content of the target product.3
Therefore, in many cases, it is necessary to recheck previ-
ously described procedures with verification of the com-
pounds formed.
Derivatives of transition metal bis(dicarbollide) com-
plexes with aryl substituents in the dicarbollide ligand belt
farthest from the metal atom are of interest for the design
of various new materials, including metal-organic frame-
works (MOFs),4 solar cells,5 and molecular switches.6—8
In contrast to the aryl derivatives of transition metal
bis(dicarbollide) complexes containing substituents in the
dicarbollide ligand belt closest to the metal atom, which
are obtained by modification of parent complexes,9—12
derivatives with aryl substituents in the farthest dicarbol-
lide ligand belt are prepared by assembling from the cor-
responding nido-carboranes on the metal ion. In this case,
derivatives with substituents at the remotest from carbon
atoms positions 9 and 12, are obtained by assembling from
relatively available 5-aryl- and 5,6-diaryl-nido-carb-
oranes,4,13 while the synthesis of derivatives with sub-
stituents at position 6 adjacent to carbon atoms requires
the use of much less available 3-aryl-nido-carboranes.14,15
The purpose of the present work is to synthesize cobalt
and nickel bis(dicarbollide) 6,6´-diphenyl derivatives and
recheck the previously described procedures with charac-
terization of all the intermediate and by-products formed.
Results and Discussion
Cobalt and nickel bis(dicarbollide) 6,6´-diphenyl
derivatives were synthesized according to Scheme 1. The
sequence includes the insertion of the BPh group into the
nido-carborane cage with the formation of 3-phenyl-ortho-
carborane, its subsequent deboronation to 3-phenyl-nido-
carborane, and the insertion of the metal atom to form
the corresponding metal complexes [6,6´-Ph2-3,3´-Co-
(1,2-C2B9H10)2]– (see Ref. 14) and [6,6´-Ph2-3,3´-
Ni(1,2-C2B9H10)2] (see Ref. 6).
The preparation of 3-phenyl-ortho-carborane by the
insertion of phenylboron dichloride PhBCl2 into the di-
carbollide anion was described already 50 years ago,14
however, it was characterized only by elemental analysis
* Dedicated to Academician of the Russian Academy of Sciences
O. N. Chupakhin on the occasion of his 85th birthday.
1
data and H NMR spectroscopy. Later, a two-step syn-
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1239—1247, June, 2019.
1066-5285/19/6806-1239 © 2019 Springer Science+Business Media, Inc.

1240
Russ. Chem. Bull., Int. Ed., Vol. 68, No. 6, June, 2019
Shmal´ko et al.
Scheme 1
thesis of 3-phenyl-ortho-carborane through the inser-
tion of boron triiodide into the dicarbollide anion with
subsequent Pd-catalyzed cross-coupling of the resulting
3-iodo-ortho-carborane with phenylmagnesium bromide
PhMgBr was described. The resulting product was fully
characterized by NMR and IR spectroscopy and X-ray
diffraction analysis.15 Recently,16 the preparation of
3-phenyl-ortho-carborane by the reaction of diazonium
derivative [3-N2-1,2-C2B10H11][BF4] with phenylmag-
nesium bromide PhMgBr was described. The latter two
methods are of interest for the preparation of derivatives
with different substituents in the aryl ring, but since
phenylboron dichloride is commercially available, the
one-step method for the synthesis of 3-phenyl-ortho-
carborane is preferred.
dodecahydro-7,8-dicarba-nido-undecaborate K[7,8-
C2B9H12] (1) with n-butyllithium, with PhBCl2 in diethyl
ether leads, in addition to 3-phenyl-ortho-carborane 2
(69% yield), to three minore uncharged products. They
were isolated by column chromatography and identified
as nido-carborane 9- and 10-diethyloxonium derivatives
[9-Et2O-7,8-C2B9H11] (3a) and [10-Et2O-7,8-C2B9H11
]
(4), as well as 9-diethyloxonium-11-chloro derivative
[9-Et2O-11-Cl-7,8-C2B9H10] (3b) (Scheme 2). If the
synthesis is carried out in a dilute solution (four-fold dilu-
tion), the yield of the target 3-phenyl-ortho-carborane 2
decreases to 60%, while the yields of by-products 3 and 4
increase to 9 and 11%, respectively.
The formation of nido-carborane diethyloxonium
derivatives results from the nucleophilic substitution re-
action initiated by PhBCl2 as a Lewis acid.17 Thus,
the formation of similar tetrahydrofuran derivatives of
We found that the reaction of the deprotonated form
of nido-carborane, obtained by treatment of potassium
Scheme 2

Synthesis of [6,6´-Ph2-3,3´-M(1,2-C2B9H10)2]– Russ. Chem. Bull., Int. Ed., Vol. 68, No. 6, June, 2019
1241
nido-carborane in its reaction with FeCl3 in THF was
described earlier.18 Note that no formation of by-products
is observed when the insertion reaction is carried out in
toluene, but the yield of 3-phenyl-ortho-carborane 2 de-
creases to 43%.
The symmetrically substituted nido-carborane 10-di-
ethyloxonium derivative 4 was obtained earlier in ~25%
yield in the acid-catalyzed reaction of nido-carborane with
formaldehyde or acetaldehyde in the presence of diethyl
ether.19 We obtained a single crystal of 4 and its molec-
ular structure was determined by X-ray diffraction ana-
lysis (Fig. 1).
The B(10)—O(1) bond length is 1.508 Å, which is
slightly shorter than in the known oxonium derivatives of
polyhedral boron hydrides (1.517—1.553 Å),20—29 while
the C—O bonds (1.463(3) and 1.478(4) Å) are of the same
order as in other oxonium derivatives (1.417—1.515 Å).
The orientation of the substituent at B(10) atom is such
that the torsion angle B(9)—B(10)—O(1)—C(3) is
–60.97(19)°. This orientation seems to be additionally
stabilized by the detected shortened contacts H(9)…H(4C)
and H(6)…H(1A) (2.26(2) and 2.49(2) Å, respectively).
Since the possibility of attractive C—H…H—B interactions
was repeatedly demonstrated earlier,30—33 we performed
quantum chemical calculations for compound 4. The
calculated geometry slightly differs from the experimental
one: the torsion angle B(9)—B(10)—O(1)—C(3) is –40.8°,
the distances H(9)…H(4C) and H(6)…H(1A) are 2.47 and
2.25 Å, respectively. However, two shortened contacts
were found in both the calculation and the experiment.
A topological analysis of the electron density showed that
both contacts are attractive and are characterized by the
energies of –1.9 and –0.8 kcal mol–1 for H(9)…H(4C)
and H(6)…H(1A), respectively.
The unsymmetrically substituted nido-carborane 9-di-
ethyloxonium derivative 3a was not earlier described, its
structure was proved by the NMR spectroscopy data.
The 11B NMR spectrum consists of a singlet at δ 8.1 and
seven doublets at δ –13.5, –19.1, –21.5, –23.9, –25.3,
–33.2, and –39.5 with a ratio of integral intensities of
1 : 2 : 1 : 1 : 1 : 1 : 1 : 1. The 1H NMR spectrum contains
signals at δ 4.50 and 1.48 characteristic of the ethyl groups,
signals for nonequivalent CH groups of the carborane cage
at δ 1.98 and 1.90, and a broad signal for the proton of the
BHB bridge at δ –2.55. In the 13C NMR spectrum, the
signals for the ethyl groups are found at δ 78.3 and 13.3,
while the signals for the carbon atoms of the carborane
cage, at δ 41.7 and 34.0. The chemical shifts of the signals
for the methylene groups bonded to the oxygen atom are
the same in derivatives 3a and 4. As it was shown earlier,34
the position of these signals is a good indicator of the
strength of the electron-donating effect of polyhedral
C(4)
C(3)
B(9)
B(10)
C(8)
O(1)
C(1)
C(7)
B(11)
C(2)
B(4)
B(5)
B(3)
B(6)
B(2)
B(1)
Fig. 1. A general view of molecule 4 in the representation of atoms by thermal displacement ellipsoids with a 50% probability. The
...
dashed lines show attractive noncovalent H H contacts.
Note. Figures 1 and 2 are available in full color on the web page of the journal (http://www.link.springer.com).

1242
Russ. Chem. Bull., Int. Ed., Vol. 68, No. 6, June, 2019
Shmal´ko et al.
Scheme 4
boron hydrides. Thus, it can be suggested that the elec-
tronic effects of the nido-carborane cage substituted at
positions 9 and 10 are very close.
Cyclic oxonium derivatives of polyhedral boron hydr-
ides are well studied because they are convenient starting
compounds for the preparation of various functional de-
rivatives.35—37 At the same time, there are only a few
published examples of diethyloxonium derivatives of
polyhedral boron hydrides, including derivatives of closo-
decaborate38 and closo-dodecaborate39 anions, nido-
carborane,19 and some metallaboranes29 and metalla-
carboranes.40,41 In contrast to cyclic oxonium derivatives,
the reactions of diethyloxonium derivatives with nucleo-
philes proceed with the elimination of one ethyl group to
give the corresponding ethoxy derivatives.38,41 We found
that reflux of diethyloxonium derivatives 3a and 4 in
pyridine leads to the elimination of an ethyl group and
formation of ethoxy derivatives [9-EtO-7,8-C2B9H11]– (5)
and [10-EtO-7,8-C2B9H11]– (6), respectively, which were
isolated as tetramethylammonium salts (Scheme 3).
–16.2, –21.5, –35.0, and –36.5 with a ratio of integral
intensities of 1 : 2 : 2 : 2 : 1 : 1. The 1H NMR spectrum in
acetone-d6 exhibits signals for the phenyl group at δ 7.50
and 7.11, for the CH groups of the carborane cage at δ 1.88,
and a broad signal for the proton of the BHB bridge at
δ –2.53.
6,6´-Diphenyl derivative of cobalt bis(dicarbollide)
[6,6´-Ph2-3,3´-Co(1,2-C2B9H10)2]– (8) was obtained by
deprotonation of nido-carborane 7 in 40% aqueous NaOH,
followed by the reaction of the resulting dicarbollide anion
with CoCl2•6H2O, and isolated as a tetramethylammo-
nium salt (Scheme 5). This method is much more conve-
nient than the synthesis described earlier,14 which uses
sodium hydride and anhydrous CoCl2, and gives a some
higher yield of the target product (68% compared to 62%
for the anhydrous method).
Scheme 3
Scheme 5
i. 1) pyridine, Δ; 2) Me4NCl, H2O.
The transformation of the diethyloxonium substituent
into the ethoxy one leads to a noticeable upfield shift of
the methylene group signals by about 1 and 15 ppm in the
1H and 13C NMR spectra, respectively. At the same time,
a slight downfield shift (~1—2 ppm) of the signals corres-
ponding to the substituted boron atoms is observed in the
11B NMR spectra.
The 11B NMR spectrum of Me4N[8] in acetone-d6
exhibits a singlet at δ –14.1 and four doublets at δ 4.8, 2.1,
–5.6, and –16.4 with a ratio of integral intensities of
2 : 2 : 8 : 2 : 4. The 1H and 13C NMR spectra exhibit sig-
nals for the phenyl groups, as well as for the CH groups
of the carborane cage at δ 4.28 and 53.7, respectively.
The structure of Me4N[8] was established by X-ray
diffraction analysis (Fig. 2). The symmetrically indepen-
dent part of the unit cell contains one molecule of
the Me4N+ cation and two [6,6´-Ph2-3,3´-Co(1,2-
C2B9H10)2]– halves of anions A and B. The dicarbollide
ligands in both anions are rotated by 180° relative to each
other and form a transoid conformation. The phenyl
The preparation of 3-phenyl-nido-carborane [3-Ph-
7,8-C2B9H11]– was also described previously,14 but it was
characterized only by 1H NMR spectroscopy data. We
have found that reflux of 3-phenyl-ortho-carborane with
NaOH in ethanol gives the corresponding nido-carborane
[3-Ph-7,8-C2B9H11]– (7) in high yield, which was isolated
as a trimethylammonium salt (Scheme 4).
The 11B NMR spectrum of (Me3N)[7] in CDCl3 ex-
hibits a singlet at δ –9.9 and five doublets at δ –10.6,

Synthesis of [6,6´-Ph2-3,3´-M(1,2-C2B9H10)2]– Russ. Chem. Bull., Int. Ed., Vol. 68, No. 6, June, 2019
1243
C(5A)
C(4A)
C(6A)
B(10A)
B(9A)
C(7A)
C(8A)
B(5A)
C(3A)
B(12A)
B(8A)
B(6A)
B(11A)
C(1A)
B(4A)
B(7A)
C(2A)
Co(3)
C(2)
B(7)
B(4)
B(8)
C(1)
B(6)
B(12)
C(3)
B(11)
C(8)
B(9)
C(7)
B(5)
B(10)
C(4)
C(5)
C(6)
Fig. 2. A general view of the [6,6´-Ph2-3,3´-Co(1,2-C2B9H10)2]– anion (8) in the representation of atoms by thermal displacement
ellipsoids with a 50% probability.
substituents in each anion are parallel to each other, but
their rotation relative to the carborane cage is different in
different anions (the torsion angles С(1)—B(6)—C(3)—C(4)
are 148.8(3) and 86.1(3)° for A and B, respectively). The
tural units in solvates and cocrystals was repeatedly ob-
served earlier44—47 and is at least one of the main driving
forces for the formation of such crystal structures. In
the crystal, the Н…π and СН…ВН contacts mentioned
above (the shortest distances: H(7A)…С(8´), 2.81 Å,
C(2)—H(2)…H(8´)—B(8´), 2.35 Å) cause the formation
of chains along the c axis from alternating anions A and
B rotated by ~90° relative to each other. Apparently, this
explains the different relative orientation of phenyl sub-
stituents in anions A and B, contributing to the formation
of intermolecular interactions.
In contrast to cobalt 6,6´-diphenylbis(dicarbollide), the
preparation for nickel 6,6´-diphenylbis(dicarbollide) was
described earlier only as a synthetic scheme and a figure of
the crystal structure in the conference reports6 without any
characterization. We found that the reaction of nickel acet-
ylacetonate Ni3(acac)6 with deprotonated 3-phenyl-nido-
carborane in tetrahydrofuran leads to nickel(III) 6,6´-di-
phenylbis (dicarbollide) (9), the oxidation of which with
ferric(III) chloride FeCl3 in acetonitrile gives the desired
nickel(IV) 6,6´-diphenylbis(dicarbollide) (10) (Scheme 6).
... ...
H HCPh and BH HCPh contacts in the anions A
Ccarb
and B are 2.49 and 2.41 Å and 2.29 and 2.49 Å, respectively,
which is comparable with the length of the corresponding
contacts in 3-phenyl-ortho-carborane 2 (2.48 and 2.43 Å)15
and slightly longer than in 1-phenyl-ortho-carborane
(2.04 and 2.15 Å).30,42,43 The B(6)—C(Ph) bond lengths
in the anions A and B are 1.574(2) and 1.576(2) Å, respec-
tively, which is somewhat larger than the length of the
corresponding B(3)—C(Ph) bond in the structure of
3-phenyl-ortho-carborane 2 (1.565 Å).15
The crystal structure is stabilized by relatively weak
Н…π and СН…ВН interactions existing between the
cation and the anion, as well as between dicarbollide
anions A and B; in this case, no shortened contacts are
formed between the same type of anions (А…А or В…В).
The presence of interactions between two symmetrically
independent molecules in a crystal or between two struc-

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Russ. Chem. Bull., Int. Ed., Vol. 68, No. 6, June, 2019
Shmal´ko et al.
Scheme 6
by a dropwise addition of a solution of PhBCl2 (6.20 mL, 7.63 g,
48.0 mmol) in diethyl ether (10 mL). The mixture was stirred for
100 h, the reaction progress was monitored by thin layer chrom-
atography. Then, the reaction mixture was quenched with water
(100 mL). The organic fraction was separated, dried with Na2SO4,
filtered, and concentrated on a rotary evaporator. The residue
was subjected to column chromatography (eluent chloroform—
hexane, 3 : 1). The first, second, third, and fourth fractions were
collected and concentrated on a rotary evaporator to obtain
compounds 2 (5.82 g, 69%), 3a (0.24 g, 3%), 3b (0.03 g, 0.3%),
and 4 (0.38 g, 5%), respectively.
B. A 2.5 М solution of BuLi in hexane (1.32 mL, 3.3 mmol)
was added dropwise to a suspension of compound 1 (0.45 g,
3.00 mmol) in toluene (50 mL) at –30 °C. The reaction mixture
was allowed to warm-up to room temperature, then cool to
–30 °C, followed by a dropwise addition of a solution of 97%
PhBCl2 (0.44 mL, 0.54 g, 3.3 mmol) in toluene (5 mL). The
mixture was stirred for 100 h, the reaction progress was monitored
by thin layer chromatography. Then, the reaction mixture was
concentrated on a rotary evaporator. The residue was dissolved
in chloroform (25 mL) and passed through a layer of silica gel
on a Schott filter. The system was washed with chloroform until
the product was not detected by thin layer chromatography. The
yield of compound 2 was 0.27 g (43%). The spectral data of
compound 2 agree with the literature data.15
The 11B NMR spectrum of compound 10 in CDCl3
exhibits a set of doublets at δ 20.8, 18.9, 4.9, and 1.9, as
well as overlapped doublet and singlet at δ –7.1 with a total
1
ratio of integral intensities of 2 : 2 : 4 : 4 : 6. The H and
13C NMR spectra exhibit signals for the phenyl groups, as
well as for the CH groups of the carborane cage at δ 4.47
and 67.3, respectively.
Thus, we synthesized 6,6´-diphenyl derivatives of cobalt
and nickel bis(dicarbollide), the separate steps of which
were described in the literature,6,14 the earlier unknown
products were isolated and characterized. The by-products
of the insertion of PhBCl2 into the nido-carborane cage,
the nido-carborane diethyloxonium derivatives [9-Et2O-
7,8-C2B9H11] and [10-Et2O-7,8-C2B9H11], were detected
and characterized. Treatment of the latter with pyridine
Compound 3a. 1H NMR (CDCl3), δ: 4.50 (m, 4 Н, OCH2CH3,
J = 7 Hz); 1.98 (br.s, 1 Н, СHcarb); 1.90 (br.s, 1 Н, СHcarb), 1.48
(t, 3 Н, OCH2CH3, J = 7 Hz); –2.55 (br.s, 1 H, BHBbridge).
13C{1H} NMR (CDCl3), δ: 78.3 (OCH2CH3), 41.7 (Сcarb), 34.0
(Сcarb), 13.3 (OCH2CH3). 11B NMR (CDCl3), δ: 8.1 (s, 1 В);
–13.5 (d, 2 В, J = 138 Hz); –19.1 (d, 1 В, J = 165 Hz); –21.5
(d, 1 В, J = 154 Hz); –23.9 (d, 1 В, J = 158 Hz); –25.3 (d, 1 В,
J = 180 Hz); –33.2 (dd, 1 В, J1 = 126 Hz, J2 = 57 Hz); –39.5
(d, 1 В, J = 140 Hz). MS (EI), found m/z 206 [М]+; C6H21B9O;
calculated for C6H21B9O: [М]+ = 206.
leads to the elimination of one ethyl group to give the
–
corresponding ethoxy derivatives [9-EtO-7,8-C2B9H11
]
Compound 3b. 1H NMR (CDCl3), δ: 4.49 (q, 2 Н, OCH2CH3,
J = 7 Hz); 4.48 (q, 2 Н, OCH2CH3, J = 7 Hz);1.88 (br.s, 1 Н,
СHcarb); 1.73 (br.s, 1 Н, СHcarb); 1.47 (t, 3 Н, OCH2CH3,
J = 7 Hz); –2.37 (br.s, 1 H, BHBbridge). 13C{1H} NMR (CDCl3),
δ: 78.0 (OCH2CH3), 40.8 (Сcarb), 32.5 (Сcarb), 13.3 (OCH2CH3).
11B NMR (CDCl3), δ: 8.8 (s, 1 В, B—O); –0.9 (s, 1 В, B—Cl);
–13.7 (d, 2 В, J = 144 Hz); –19.6 (d, 2 В, J = 157 Hz); –25.3
(d, 1 В, J = 138 Hz); –29.4 (d, 1 В, J = 156 Hz); –33.8 (dd, 1 В,
J1 = 130 Hz, J2 = 47 Hz); –39.9 (d, 1 В, J = 143 Hz).
and [10-EtO-7,8-C2B9H11]–.
Experimental
Potassium dodecahydro-7,8-dicarba-nido-undecaborate K[7,8-
C2B9H12] (1) was obtained as described in the literature.48
Dichlorophenylborane PhBCl2 (Acros Organics) was used with-
out additional purification. The reactions progress was monitored
by thin layer chromatography on Kieselgel 60 F245 plates
(Merck), visualizing by a 0.5% solution of PdCl2 in 1% HCl in
a MeOH—H2O solvent mixture (10 : 1). Acros Organics silica
gel, 0.060–0.200 mm, 60 Å, was used for column chromato-
graphy. 1H, 11B, 11B{1H}, and 13C{1H} NMR spectra were re-
corded on a Bruker Avance 400 spectrometer. Chemical shifts
Compound 4. 1H NMR (CDCl3), δ: 4.50 (q, 4 Н, OCH2CH3,
J = 7 Hz); 2.00 (br.s, 2 Н, СHcarb); 1.54 (t, 3 Н, OCH2CH3,
J = 7 Hz); 0.03 (br.s, 1 H, BHBbridge). 13C{1H} NMR (CDCl3),
δ: 79.9 (OCH2CH3), 42.9 (Сcarb), 12.9 (OCH2CH3). 11B NMR
(CDCl3), δ: –10.1 (s, 1 В); –12.6 (d, 2 В, J = 139 Hz); –16.6
(d, 2 В, J = 137 Hz); –21.7 (d, 2 В, J = 146 Hz); –22.1 (d, 1 В);
–39.5 (d, 1 В, J = 138 Hz). MS (EI), found m/z 206 [М]+;
C6H21B9O; calculated for C6H21B9O: [М]+ = 206.
Tetramethylammonium 9-ethoxyundecadecahydro-7,8-di-
carba-nido-undecaborate (5). A solution of compound 3 (0.18 g,
0.9 mmol) in pyridine (25 mL) was refluxed for 24 h, the progress
of dealkylation reaction was monitored by thin layer chromato-
graphy. The reaction mixture was concentrated on a rotary
evaporator, the residue was subjected to column chromatography
(eluent dichloromethane—acetone, 1 : 1). The first fraction
contained unreacted starting compound 3, the second fraction
was concentrated on a rotary evaporator, the residue was dissol-
ved in water (10 mL), the product was precipitated with a solu-
tion of Me4NCl (0.12 g, 1.3 mmol) in water (5 mL). The preci-
1
are given relative to Me4Si (for H and 13C NMR spectra) and
BF3•Et2O (for 11B NMR spectra). 11B NMR spectra were used
to determine the splitting pattern of boron signals. Mass spectra
were obtained on a Kratos MS 890 mass spectrometer, high
resolution mass spectra (HRMS) were obtained on a Bruker
Daltonics microOTOF II mass spectrometer.
3-Phenyl-1,2-dicarba-closo-dodecarborane (2), 9-diethyl-
oxonium-7,8-dicarba-nido-undecarborane (3a), and 10-diethyl-
oxonium-7,8-dicarba-nido-undecarborane (4). А. A 2.5 М solution
of BuLi in hexane (17.6 mL, 44.00 mmol) was added dropwise
to a suspension of compound 1 (5.94 g, 40.0 mmol) in diethyl
ether (150 mL) at –50 °C. The reaction mixture was allowed to
warm-up to room temperature, then cool to –30 °C, followed

Synthesis of [6,6´-Ph2-3,3´-M(1,2-C2B9H10)2]– Russ. Chem. Bull., Int. Ed., Vol. 68, No. 6, June, 2019
1245
pitate was collected by filtration, washed, and dried over P2O5
(CD3COCD3), δ: 4.8 (d, 2 В, J = 148 Hz); 2.1 (d, 2 В, J = 134 Hz);
–5.6 (d, 8 В, J = 139 Hz); –14.1 (s, 2 В), –16.4 (d, 4 В, J = 151 Hz).
Potassium 6,6´-diphenyleicosahydro-1,1´,2,2´-tetracarba-3-
commo-nickela-closo-tricosaborate (9). Potassium tert-butoxide
(0.90 g, 8.0 mmol) was added to a solution of compound 5 (0.27 g,
1.0 mmol) in THF (50 mL) and the mixture was refluxed for 3 h.
After the addition of Ni3(acac)6 (0.39 g, 1.5 mmol), the reflux
was continued for another 14 h, monitoring the reaction progress
by thin layer chromatography. Then the reaction mixture was
concentrated on a rotary evaporator. The residue was dissolved
in water (50 mL), the product was extracted with dichlorometh-
ane (3×50 mL). The organic fractions were separated, combined,
dried with Na2SO4, filtered, and concentrated on a rotary
evaporator to obtain compound 9 (0.19 g, 74%). 11B NMR
(CD3COCD3), δ: 15.0, 2.3, –53.3.
1
to obtain compound 5 (0.12 g, 54%). H NMR (CD3COCD3),
δ: 3.45 (m, 2 Н, OCH2CH3); 3.39 (s, 12 Н, (CH3)4N); 1.53 (br.s,
1 Н, СHcarb); 1.34 (br.s, 1 Н, СHcarb); 0.99 (t, 3 Н, OCH2CH3,
J = 7 Hz); –2.91 (br.s, 1 H, BHBbridge). 13C{1H} NMR
(CD3COCD3), δ: 63.7 (OCH2CH3), 55.9 ((CH3)4N), 40.6
(Сcarb), 26.7 (Сcarb), 18.0 (OCH2CH3). 11B NMR (CD3COCD3),
δ: 10.5 (s, 1 В); –12.3 (d, 1 В, J = 135 Hz); –16.2 (d, 1 В,
J = 135 Hz); –19.7 (d, 1 В, J = 162 Hz); –21.6 (d, 1 В, J = 152 Hz);
–25.5 (d, 2 В, J = 137 Hz); –31.0 (d, 1 В, J = 122 Hz); –38.6
(d, 1 В, J = 136 Hz). HRMS (ESI), found m/z 178.2076 [М]+;
C4H16B9O; calculated for C4H16B9O: [М]+ = 178.2084.
Tetramethylammonium 10-ethoxyundecadecahydro-7,8-di-
carba-nido-undecaborate (6). The synthesis was carried out
similarly to the procedure described above using compound 4
(0.23 g, 1.1 mmol) and Me4NCl (0.16 g, 1.7 mmol). The yield
of compound 6 was 0.14 g (50%). 1H NMR (CD3COCD3), δ:
3.47 (m, 2 Н, OCH2CH3); 3.41 (s, 12 Н, (CH3)4N); 1.44 (br.s,
2 Н, СHcarb); 1.01 (t, 3 Н, OCH2CH3, J = 7 Hz); –0.55
(br.s, 1 H, BHBbridge). 13C{1H} NMR (CD3COCD3), δ: 65.6
(OCH2CH3); 56.0 ((CH3)4N); 38.7 (Сcarb); 17.9 (OCH2CH3).
11B NMR (CD3COCD3), δ: –9.3 (s, 1 В); –12.4 (d, 2 В,
J = 135 Hz); –17.4 (d, 2 В, J = 129 Hz); –24.1 (d, 2 В,
J = 151 Hz); –25.4 (d, 1 В, J = 171 Hz); –40.6 (d, 1 В,
J = 138 Hz). HRMS (ESI), found m/z 178.2076 [М]+; C4H16B9O;
calculated for C4H16B9O: [М]+ = 178.2084.
6,6´-Diphenyl-1,1´,2,2´-tetracarba-3-commo-nickela-closo-
tricosaborane (10). A solution of FeCl3 (0.18 g, 1.1 mmol) in
acetonitrile (10 mL) was added dropwise to a solution of com-
pound 8 (0.19 g, 0.4 mmol) in acetonitrile (50 mL) and the
mixture was stirred for 24 h, monitoring the reaction progress by
thin layer chromatography. Then, the reaction mixture was
concentrated on a rotary evaporator. The residue was subjected
to column chromatography (eluent dichloromethane). The first
fraction was collected and concentrated on a rotary evaporator
to obtain compound 10 (0.16 g, 91%). 1H NMR (CDCl3), δ:
7.62 (d, 4 Н, о-Harom, J = 7.1 Hz); 7.44 (t, 2 Н, p-Harom
,
Trimethylammonium 3-phenylundecadecahydro-7,8-dicarba-
nido-undecaborate (7). Sodium hydroxide (0.86 g, 21.5 mmol)
was added to a solution of compound 2 (1.51 g, 7.2 mmol) in
ethanol (150 mL). The mixture was refluxed for 16 h, the reaction
progress was monitored by thin layer chromatography. Then, the
reaction mixture was neutralized with aqueous HCl to neutral
pH, filtered, and concentrated on a rotary evaporator. The resi-
due was dissolved in water (40 mL), the product was precipi-
tated with a solution of Me3NHCl (1.05 g, 11.0 mmol) in water
(10 mL). The resulting oily layer was extracted with dichloro-
methane (50 mL). The organic fraction was separated, dried with
Na2SO4, filtered, and concentrated on a rotary evaporator to
J = 7.3 Hz); 7.37 (dd, 4 Н, m-Harom, J1 = 7.1 Hz, J1 = 7.3 Hz);
4.47 (br.s, 4 Н, СHcarb). 13C{1H} NMR (CDCl3), δ: 133.7
(Сarom), 130.4 (p-Сarom), 128.5 (Сarom), 67.3 (Сcarb). 11B NMR
(CDCl3), δ: 20.8 (d, 2 В, J = 181 Hz); 18.9 (d, 2 В, J = 170 Hz);
4.9 (d, 4 В, J = 140 Hz); 1.9 (d, 4 В, J = 128 Hz); –7.1 (d + s,
6 В). HRMS (ESI), found: m/z 475.3506 [М]–; C16H30B18Ni;
calculated for C16H30B18Ni: [М]– = 475.3522.
X-ray diffraction analysis of compounds 4 and Me4N[8] was
carried out on an APEX II CCD diffractometer (λ(Mo-Kα) =
= 0.71073 Å, graphite monochromator, ω-scan technique) at 120 K.
Single crystals of 4 and 8 suitable for X-ray diffraction experiment
were obtained by crystallization from hexane—dichloromethane and
hexane—dichloromethane—acetone solvent mixtures, respectiv-
ely. The processing of the initial arrays of measured intensities was
carried out using the SAINT and SADABS programs incorporat-
ed into the APEX2 software package.49 The structures were solved
by the direct method and refined by the full-matrix least squares
method in anisotropic approximation for non-hydrogen atoms
with respect to F 2hkl. All the calculations were carried out using
the SHELXTL and OLEX2 software packages.50,51 The main
crystallographic parameters are given in Table 1. Both structures
are registered in the the Cambridge Crystallographic Data Center
(CCDC 1873049 for 4 and 1903011 for Me4N[8]).
Quantum chemical calculations. The molecule 4 was optimized
in the PBE0/6-311G(df,pd) approximation, using the GAUSSIAN
program.52 The reliability of this approximation for modeling the
structure of a wide range of organic and organoelement com-
pounds has been demonstrated in a number of papers.53—56 The elec-
tron density distribution obtained in the calculations was analyzed in
the framework of the R. Bader "Atoms in Molecules" theory,57 using
the AIMALL program.58 The energy of contacts was evaluated
by its correlation with the potential energy density function V(r)
at the bond critical point (Eint = 1/2V(r)),59,60 which is widely
used for studies of various types of interactions.61—65
1
obtain compound 7 (1.67 g, 86%). H NMR (CD3COCD3), δ:
7.50 (d, 2 Н, Harom, J = 4 Hz); 7.11 (m, 3 Н, Harom); 3.11 (s, 9 Н,
(CH3)3N); 1.88 (br.s, 2 Н, СHcarb); –2.53 (br.s, 1 H, BHBbridge).
11B NMR (CDCl3), δ: –9.9 (s, 1 В); –10.6 (d, 2 В, J = 147 Hz);
–16.2 (d, 2 В, J = 138 Hz); –21.5 (d, 2 В, J = 145 Hz); –35.0
(d, 1 В, J = 136 Hz); –36.5 (d, 1 В, J = 149 Hz).
Tetramethylammonium 6,6´-diphenyleicosahydro-1,1´,2,2´-
tetracarba-3-commo-cobalta-closo-tricosaborate (Me4N[8]).
Compound 5 (1.16 g, 4.3 mmol) was added to a freshly prepared
hot 40% solution of NaOH (25 mL) in water, the mixture was
stirred until the salt was completely dissolved and evolution of
Me3N ceased. Next, CoCl2•6H2O (2.38 g, 10.0 mmol) was
added to the mixture and it was stirred for 4 h. After the addition
of (100 mL), the organic phase was separated, the aqueous frac-
tion was extracted with diethyl ether (4×50 mL). The combined
organic fractions were dried with Na2SO4, filtered, and concen-
trated on a rotary evaporator. The residue was dissolved in water
(50 mL) and a solution of Me4NBr (1.54 g, 10.0 mmol) in water
(10 mL) was added. The precipitate was collected by filtration,
washed with water, and dried over P2O5 to obtain compound 8
(0.80 g, 68%) as an orange powder. 1H NMR (CD3COCD3), δ:
7.65 (m, 4 Н, Harom); 7.25 (m, 6 H, Harom); 4.28 (br.s, 4 Н,
СHcarb); 3.44 (s, 12 Н, (CH3)4N+); 4.0—1.0 (m, 16 Н, BH).
13C{1H} NMR (CD3COCD3), δ: 133.2 (Сarom), 127.6 (Сarom),
127.3 (Сarom), 55.1 ((CH3)4N+); 53.7 (Сcarb). 11B NMR
This work was financially supported by the Russian
Foundation for Basic Research (Project Nos 18-33-00336

1246
Russ. Chem. Bull., Int. Ed., Vol. 68, No. 6, June, 2019
Shmal´ko et al.
Table 1. Crystallographic data and parameters of X-ray diffraction experiment for compound 4 and Me4N[8]
Parameter
4
Me4N[8]
Molecular formula
C6H21B9O
206.52
Orthorhombic
Pbca
13.544(3)
13.339(3)
13.996(3)
90
C16H30B18Co–•C4H12N+
550.05
Molecular weight
Crystal system
Triclinic
Space group
P–1
a/Å
10.2489(11)
10.7454(11)
14.3906(15)
89.435(2)
72.390(2)
77.605(2)
1472.8(3)
2
b/Å
c/Å
α/deg
β/deg
90
90
γ/deg
V/Å3
2528.5(10)
8
Z
dcalc/g cm–3
1.085
1.240
Absorption coefficient, μ/mm–1
F(000)
0.055
0.598
880
s572
θ range of scanning/deg
Number of reflections
measured
independent
Rint
2.59—27.00
1.49—29.01
19328
2759
35781
7821
0.0477
100
0.0257
99.8
Completeness of reflection array (%)
Number of refined parameters
Number of reflections with I ≥ 2σ(I)
GOOF
191
448
2183
6953
1.031
1.088
Convergence (R1(F))a for reflections with I ≥ 2σ(I)
Convergence for all reflections (wR2(F2))b
Residual electron density
(ρmax/ ρmin)/e Å–3
0.0504
0.1472
0.406/–0.216
0.0305
0.0791
0.400/–0.296
a R1 = ∑ |Fo – |Fc||/∑(Fo).
b wR2 = (∑[w(Fo2 – Fc2)2]/∑[w(Fo2)2]1/2
.
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and 18-33-20115). X-ray diffraction data and NMR spec-
tra were obtained using equipment of the X-Ray
Structural Center of the A. N. Nesmeyanov Institute of
Organoelement Compounds of the Russian Academy
of Sciences.
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Received November 27, 2018;
in revised form March 19, 2019;
accepted April 4, 2019