Synthesis of 9,912,12-substituted cobalt bis(dicarbollide) derivatives

Article abstract of DOI:10.1007/s11172-015-0924-4

A partial degradation of 9,12-disubstituted derivatives of ortho-carboranes 9,12-X₂-1,2-C₂B₁₀H₁₀ (X = Br, Alk, Ar) led to the corresponding substituted nido-carboranes [5,6-X₂-7,8-C₂B₉

Full text of DOI:10.1007/s11172-015-0924-4

7
12
Russian Chemical Bulletin, International Edition, Vol. 64, No. 3, pp. 712—717, March, 2015
Synthesis of 9,9´,12,12´ꢀsubstituted cobalt bis(dicarbollide) derivatives*
S. A. Anufriev, I. B. Sivaev, and V. I. Bregadze
A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
2
8 ul. Vavilova, 119991 Moscow, Russian Federation.
Eꢀmail: sivaev@ineos.ac.ru
A partial degradation of 9,12ꢀdisubstituted derivatives of orthoꢀcarboranes 9,12ꢀX ꢀ1,2ꢀ
2
C B H (X = Br, Alk, Ar) led to the corresponding substituted nidoꢀcarboranes [5,6ꢀX ꢀ7,8ꢀ
2
10 10
2
–
C B H ] , which on the reaction with cobalt(II) chloride gave new 9,9´,12,12´ꢀtetrasubstitutꢀ
2
9
10
–
ed derivatives of cobalt bis(dicarbollide) [9,9´,12,12´ꢀX ꢀ3,3´ꢀCo(1,2ꢀC B H ) ] .
4
2
9
9 2
Key words: orthoꢀcarboranes, nidoꢀcarboranes, cobalt bis(dicarbollide), cobalt derivatives.
In 2014, 50 years have passed since discovery of first
and 8´ꢀpositioned substituents (Cl, Br, I, OH) in cobalt
bis(dicarbollide) on the crystal structure and electroconꢀ
ductivity of molecular conductors based on tetrathiafulꢀ
metallacarboranes, one of which was cobalt bis(dicarbollꢀ
1
ide). Due to a number of unique properties, such as high
7
—11
chemical stability, wide possibilities of modification via
substitution of hydrogen atoms in the carborane cage,
low nucleophilicity, as well as due to various prospects
valene radical cation salts and its derivatives.
There is
much less information on the influence of substituents at
positions 9, 9´, 12, and 12´ of the metallacarborane cage
1
2
of its practical application, cobalt bis(dicarbollide)
on the structure and properties of molecular conductors.
–
[
3,3´ꢀCo(1,2ꢀC B H ) ] became the most studied
Therefore, the purpose of the present work is the synthesis
of new 9,9´,12,12´ꢀtetrasubstituted derivatives of cobalt
bis(dicarbollide).
2
9
11 2
among metallacarboranes and one of the most studied
polyhedral boron hydrides.2—4 Cobalt bis(dicarbollide)
derivatives are of interest for the preparation of molecular
conductors. The most widespread type of molecular conꢀ
ductors are the radical cation salts, the structure of which
is characterized by the presence of conducting stacks or
layers of organic pꢀelectron donors separated by inorganic
or organometal anions. In this case, depending on the
packing type of radical cations the crystals of molecular
organic conductors can possess various electroconducting
properties: from dielectric to metallic and even to superꢀ
conducting. As a rule, anions are not directly involved in
the conducting process, however, their size and shape conꢀ
siderably influence the packing of radical cations in the
conducting layer and, therefore, the conductivity of the
Results and Discussion
In contrast to 8,8´ꢀsubstituted derivatives, which are
formed by a direct substitution in the parent cobalt
2,13
bis(dicarbollide),
9,9´,12,12´ꢀsubstituted derivatives are
synthesized by the assemblage of the corresponding nidoꢀ
carboranes on a metal ion. nidoꢀCarboranes are obtained
by a partial degradation of 9,12ꢀdisubstituted derivatives
of orthoꢀcarborane. This approach was used earlier for
the preparation of 9,9´,12,12´ꢀtetrachloro and tetraiodo
–
derivatives [9,9´,12,12´ꢀX ꢀ3,3´ꢀCo(1,2ꢀC B H ) ]
(
4
2
9
9 2
1
4 12
X = Cl, I ). In the present work, we describe the synꢀ
5
,6
crystal.
thesis of 9,9´,12,12´ꢀtetrabromo, 9,9´,12,12´ꢀtetraalkyl,
and 9,9´,12,12´ꢀtetraaryl derivatives of cobalt bis(dicarbꢀ
ollide).
Earlier,15 9,12ꢀdibromoꢀorthoꢀcarborane (1a) was obꢀ
tained by treatment of orthoꢀcarborane with molecular
bromine in the presence of aluminum metal in carbon
disulfide. Since carbon disulfide is very toxic and requires
special precautions in handling, we carried out the process
in refluxing dichloromethane in the presence of AlCl3
Introduction of substituents in the bis(dicarbollide)
cage leads to the change in the size and shape of the anion,
that greatly affects the structure of the anionic sublattice
and, as a consequence, the conducting layer packing and
transport characteristics of the molecular conductor crysꢀ
tal as a whole. The most important parameters are the size
and the placement of substituents, as well as their ability
to form intermolecular anion—anion and anion—cation
bonds. Earlier, we have studied the influence of different 8
(
Scheme 1).
The synthesis of a number of 9,12ꢀdialkyl and 9,12ꢀdiꢀ
*
Dedicated to Academician of the Russian Academy of Sciences
aryl derivatives of orthoꢀcarborane by a Pdꢀcatalyzed crossꢀ
coupling of 9,12ꢀdiiodoꢀorthoꢀcarborane with Grignard
V. I. Minkin on the occasion of his 80th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 0712—0717, March, 2015.
066ꢀ5285/15/6403ꢀ0712 © 2015 Springer Science+Business Media, Inc.
1

Tetrasubstituted cobalt bis(dicarbollides)
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 3, March, 2015
713
Scheme 1
sequent demetallation in the presence of hydrochloric acid
Scheme 3).
(
Scheme 3
reagents under different conditions has been described
earlier.1
6—19
We obtained 9,12ꢀdialkylꢀorthoꢀcarboranes
9
,12ꢀR ꢀ1,2ꢀC B H (R = Me (2), Et (3a)) by a crossꢀ
2 2 10 10
coupling of 9,12ꢀdiiodoꢀorthoꢀcarborane (1b) with the
corresponding Grignard reagents in the presence of
1
6
(
Ph P) PdCl and CuI in diethyl ether. Similar approach
3 2 2
was also used for the preparation of 9,12ꢀdiarylꢀorthoꢀ
carboranes 4, 5a, 6, 7a (Scheme 2).
Scheme 2
Reagents: i. 4ꢀMeC H MgBr, CuI, [(Ph P) Pd]Cl , Et O;
6
4
3
2
2
2
ii. 1) EtMgI, Et O; 2) HCl/H O
2
2
The earlier unknown 5,6ꢀdisubstituted nidoꢀcarboranes
—14 were obtained upon treatment of the corresponding
,12ꢀdisubstituted orthoꢀcarboranes 2, 3a, 4, 5a, 6, 7a with
8
9
X = Br, I
NaOH in refluxing ethanol and isolated as trimethylamꢀ
monium salts (Scheme 4).
R = Me (2), Et (3a), Ph (4), 4ꢀMeC H (5a), 4ꢀMeOC H4 (6),
6
4
6
4
ꢀFC H (7a)
6 4
The 11B NMR spectra of compounds 2, 3a, 4, 5a, 6, 7a
contain a singlet for the Cꢀsubstituted boron atoms in the
region  7.2—9.5 and three doublets for the unsubstituted
Scheme 4
carborane vertices with the ratio of integral intensities
1
2
: 2 : 4 : 2. The H NMR spectra exhibit broad singlets for
the carborane CH groups in the region  3.34—3.69 and
signals of the corresponding substituents.
When 9,12ꢀdiiodoꢀorthoꢀcarborane reacted with
4
ꢀMeC H MgBr, 1ꢀiodoꢀ9,12ꢀdi(pꢀtolyl)ꢀorthoꢀcarboꢀ
6 4
rane (5b) was isolated from the reaction mixture. Its strucꢀ
1
ture was inferred from the mass spectrometry and the H
and 11B NMR spectroscopy data, which indicate the lowꢀ
1
1
ering of the molecular symmetry. Thus, in the B NMR
spectrum the signals for the substituted polyhedron vertiꢀ
ces separate and are found as two singlets at  9.5 and 6.7.
R = Br (1a, 8), Me (2, 9), Et (3a, 10), Ph (4, 11), 4ꢀMeC6H4 (5a, 12),
4
ꢀMeOC H4 (6, 13), 4ꢀFC H4 (7a, 14)
6
6
Reagents: i. 1) NaOH/EtOH; 2) Me NHCl/H O.
3
2
1
The H NMR spectrum exhibits a double set of signals for
the tolyl substituents and a signal for only one carborane
CH group. Afterwards, this suggestion was confirmed by
the transformation of compound 5b to 9,12ꢀdi(pꢀtolyl)ꢀ
orthoꢀcarborane (5a) upon treatment with EtMgI with subꢀ
The 11B NMR spectra of compounds 8—14 contain
singlets for the Cꢀsubstituted boron atoms in the region
 –(7.6—5.4) and five doublets for the unsubstituted vertiꢀ
ces with the ratio of integral intensities 2 : 2 : 1 : 2 : 1 : 1.

7
14
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 3, March, 2015
Anufriev et al.
1
The H NMR spectra exhibit broad singlets for the carboꢀ
rane CH groups in the region  1.53—1.94 and signals of
the corresponding substituents.
In conclusion, we obtained and characterized a series
of new 5,6ꢀdisubstituted nidoꢀcarborane derivatives and
9,9´,12,12´ꢀsubstituted cobalt bis(dicarbollide) derivatives.
Cobalt
9,9´,12,12´ꢀtetrabromobis(dicarbollide)
K[9,9´,12,12´ꢀBr ꢀ3,3´ꢀCo(1,2ꢀC B H ) ] (K[15]) was
Experimental
4
2
9
9 2
obtained by the reaction of Me NH[8] with CoCl •6H O
3
2
2
in 40% aqueous solution of NaOH with subsequent exꢀ
traction with diethyl ether and precipitation from water
using potassium acetate. 9,9´,12,12´ꢀTetraalkyl derivatives
Me N[9,9´,12,12´ꢀR ꢀ3,3´ꢀCo(1,2ꢀC B H ) ] (R =
All the crossꢀcoupling and complexation reactions were carꢀ
ried out under argon. Diethyl ether and 1,2ꢀdimethoxyethane
were distilled over sodium metal in the presence of benzophenone,
dichloromethane was distilled over calcium hydride. 9,12ꢀDiꢀ
4
4
2
9
9 2
1
6
20
21
iodoꢀorthoꢀcarborane (1b), 4ꢀFC H Br, and (Ph P) PdCl
6
4
3
2
2
=
Me (16), Et (17)) were obtained by the reaction of
were obtained according to procedures published earlier, anhyꢀ
drous CoCl was obtained by the reaction of CoCl •6H O with
Me NH[5,6ꢀR ꢀ7,8ꢀC B H ] (9, 10) with anhydrous
3
2
2
9
10
2
2
2
t
CoCl in 1,2ꢀdimethoxyethane using Bu OK as a base
2
SOCl . Reaction progress was monitored by thinꢀlayer chromatoꢀ
2
with subsequent precipitation from water with Me NCl.
4
graphy on Kieselgel 60 F245 plates (Merck). Silica gel from
9
,9´,12,12´ꢀTetraaryl derivatives K[9,9´,12,12´ꢀR ꢀ3,3´ꢀ
Acros Organics (0.060—0.200 mm, 60 Å) was used for column
4
1
11
11
1
13
1
19
1
Co(1,2ꢀC B H ) ] (R = Ph (18), pꢀTol (19)) were synꢀ
thesized similarly, except the precipitation step since the
potassium salts obtained are insoluble in water (Scheme 5).
chromatography. H, B, B{ H}, C{ H}, and F{ H} NMR
spectra were recorded on Bruker Avanceꢀ300, Bruker Avanceꢀ400,
and Bruker AMꢀ600 spectrometer. Chemical shifts are given
2
9
9 2
1
13
The 11B NMR spectra of compounds 16—19 contain
relative to Me Si (for H and C NMR spectra), BF •Et O (for
4 3 2
11
19
11
B NMR spectra), and CFCl (for F NMR spectra). B NMR
3
singlets for the Cꢀsubstituted boron atoms in the region

spectra were used to determine splitting patterns of boron signals
the B—H spinꢀspin coupling constants are not given because of
2.7—4.7 and five doublets for the unsubstituted vertices
(
with the ratio of integral intensities 2 : 4 : 2 : 4 : 4 : 2. The
13
11
partial overlap of signals, the C— B spinꢀspin coupling conꢀ
stants are not given because of unsatisfactory resolution of sigꢀ
nals). Mass spectra were obtained on Kratos MS 890 and Bruker
Microflex LT mass spectrometers, high resolution mass spectra
1
H NMR spectra exhibit broad singlets for the carborane
CH groups in the region  3.75—4.42 and signals of the
corresponding substituents.
Scheme 5
R = Br (8, 15), Me (9, 16), Et (10, 17), Ph (11, 18), 4ꢀMeC H4 (12, 19)
6

Tetrasubstituted cobalt bis(dicarbollides)
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 3, March, 2015
715
were obtained on a Bruker Daltonics microOTOF II mass
spectrometer.
0.16 mmol), and (Ph P) PdCl (0.09 g, 0.14 mmol). The yield of
3 2 2
1
compound 4 was 0.45 g (53%). H NMR (CDCl ), : 7.23 (m, 4 H,
3
9
,12ꢀDibromoꢀ1,2ꢀdicarbaꢀclosoꢀdodecaborane (1a). A soluꢀ
mꢀH—C H —B); 7.14 (m, 6 H, pꢀH—C H —B and oꢀH—
6
4
6
4
1
1
1
tion of Br (1.81 mL, 5.54 g, 34.67 mmol) in CH Cl (50 mL)
C H —B); 3.69 (br.s, 2 H, CHcarb). B{ H} NMR (CDCl ),
2
2
2
6
4
3
was added dropwise to a solution of 1,2ꢀC B H (5.00 g,
: 7.8 (s, 2 B); –9.2 (d, 2 B); –14.0 (d, 4 B); –16.5 (d, 2 B).
2
10 12
3
4.67 mmol) in CH Cl (50 mL) over 15 min and the mixture
1ꢀIodoꢀ9,12ꢀdi(pꢀtolyl)ꢀ1,2ꢀdicarbaꢀclosoꢀdodecaborane (5b).
Compound 5b was obtained according to the procedure similar
to that for compounds 3a,b, using Mg (0.56 g, 22.88 mmol),
pꢀMeC H Br (2.45 g, 14.30 mmol), 9,12ꢀdiiodoꢀ1,2ꢀdicarbaꢀclosoꢀ
2
2
was stirred until it became colorless. Then, more Br (1.81 mL,
5
2
.54 g, 34.67 mmol) in CH Cl (50 mL) was added dropwise
2 2
over 20 min, followed by the addition of AlCl3 (1.00 g,
.50 mmol). The reaction mixture was refluxed for 20 h. After
6
4
7
dodecaborane (1.13 g, 2.86 mmol), CuI (0.03 g, 0.16 mmol), and
the reaction was complete, the mixture was cooled and treated
with a solution of Na S O (30.00 g) in water (100 mL). The
(Ph P) PdCl (0.09 g, 0.14 mmol). The yield of compound 5b
3
2
2
1
was 0.81 g (63%). H NMR (CDCl ), : 7.12 (d, 2 H, C H ,
2
2
3
3
6
4
organic phase was separated, the aqueous fraction was extracted
with dichloromethane (3×50 mL). The organic fractions were
combined, dried with Na SO , filtered, and concentrated. The
J = 7.6 Hz); 7.07 (d, 2 H, C H , J = 7.6 Hz); 6.96 (d, 2 H, C H ,
6 4 6 4
J = 8.3 Hz); 6.94 (d, 2 H, C H , J = 8.3 Hz); 3.81 (br.s, 1 H,
6
4
CHcarb); 2.26 (s, 3 H, pꢀCH —C H —B); 2.24 (s, 3 H, pꢀCH —
2
4
3
6
4
3
1
1
1
product was recrystallized from CH Cl and dried in air to obꢀ
C H —B). B{ H} NMR (CDCl ), : 9.5 (s, 1 B); 6.7 (s, 1 B);
2
1
2
6 4 3
tain compound 1a (5.99 g, 57%). H NMR (CDCl ), : 3.70
–7.2 (d, 4 B); –10.8 (d, 2 B); –12.0 (d, 2 B). MS (EI): found:
3
11
1
–
–
(
–
br.s, CHcarb). B{ H} NMR (CDCl ), : 0.3 (s, 2 B); –7.4 (d, 2 B);
m/z 450 [M] ; C H B I; calculated 450 [M] .
3
1
14 23 10
13
14.4 (d, 4 B); –16.9 (d, 2 B). C{ H} NMR (CDCl ), : 46.5.
9,12ꢀDi(pꢀtolyl)ꢀ1,2ꢀdicarbaꢀclosoꢀdodecaborane (5a). Iodoꢀ
3
(
br.s, Ccarb).
ethane (0.34 mL, 0.65 g, 4.18 mmol) was added to a suspension
9
,12ꢀDimethylꢀ1,2ꢀdicarbaꢀclosoꢀdodecaborane (2) was obꢀ
of Mg turnings (0.16 g, 6.68 mmol) in Et O (40 mL). Two drops
2
1
6 1
tained according to the procedure published earlier. H NMR
of BrCH CH Br were added to activate Mg. The reaction mixꢀ
2
2
(
CDCl ), : 3.34 (br.s, 2 H, CH ); –0.20 (br.s, 6 H, CH —B).
ture was refluxed for 1 h, the grew turbid. Then, the mixture was
cooled, followed by the addition of a solution of compound 5b
3
carb
3
1
1
1
B{ H} NMR (CDCl ), : 7.2 (s, 2 B); –7.6 (d, 2 B); –14.1 (d, 4 B);
3
–
16.6 (d, 2 B).
(0.75 g, 1.67 mmol) in Et O (40 mL) over 15 min. The mixture
2
9
,12ꢀDiethylꢀ1,2ꢀdicarbaꢀclosoꢀdodecaborane (3a) and 9ꢀethylꢀ
was stirred for 30 min, refluxed for 4 h, cooled, and treated with
10% aqueous solution of hydrochloric acid (30 mL). The organic
fraction was separated. The aqueous fraction was extracted with
diethyl ether (3×50 mL). The organic fractions were combined,
dried with Na SO , filtered, and concentrated to obtain comꢀ
1
1
2ꢀiodoꢀ1,2ꢀdicarbaꢀclosoꢀdodecaborane (3b). Iodoethane (0.38 mL,
/3 of the total amount) was added to a suspension of Mg turnꢀ
ings (0.56 g, 22.88 mmol) in Et O (30 mL). Two drops of
BrCH CH Br were added to activate Mg. The reaction mixture
2
2
2
2
4
was refluxed until it grew turbid, then cooled, followed by
a dropwise addition of a solution of iodoethane (0.77 mL, a total
pound 5a (0.42 g, 78%).
Later, compound 5a was synthesized according to the proꢀ
cedure for compounds 3a,b, using Mg (1.11 g, 45.76 mmol),
4ꢀMeC H Br (4.89 g, 28.60 mmol), 9,12ꢀdiiodoꢀ1,2ꢀdicarbaꢀclosoꢀ
of 2.23 g, 14.30 mmol) in Et O (30 mL) over 20 min. The mixꢀ
2
ture was refluxed for 1 h and cooled, followed by a dropwise
6
4
addition of a solution of 9,12ꢀdiiodoꢀ1,2ꢀdicarbaꢀclosoꢀdodeꢀ
dodecaborane (2.26 g, 5.72 mmol), CuI (0.06 g, 0.32 mmol), and
caborane (1.13 g, 2.86 mmol) in Et O (30 mL) over 20 min.
(Ph P) PdCl (0.18 g, 0.28 mmol). The yield of compound 5a
2
3
2
2
Then, the solution was stirred for 30 min, followed by the addiꢀ
tion in one portion of CuI (0.03 g, 0.16 mmol) and (Ph P) PdCl
2
was 1.35 g (73%). The spectral data corresponded to those pubꢀ
lished earlier.
1
8
3
2
(
0.09 g, 0.14 mmol). The solution gradually turned black. The
9,12ꢀBis(4ꢀmethoxyphenyl)ꢀ1,2ꢀdicarbaꢀclosoꢀdodecaborane
(6) was synthesized according to the procedure similar to that for
compounds 3a,b, using 0.50 M solution of 4ꢀMeOC H MgBr in
reaction mixture was refluxed for 40 h. After the reaction was
complete, the mixture was cooled and treated with 10% aqueous
solution of hydrochloric acid (30 mL). The organic phase was
separated. The aqueous fraction was extracted with diethyl ether
6
4
THF (2.11 g, 10.00 mmol; 20.00 mL of solution), 9,12ꢀdiiodoꢀ
1,2ꢀdicarbaꢀclosoꢀdodecaborane (0.79 g, 2.00 mmol), CuI (0.03 g,
0.16 mmol), and (Ph P) PdCl (0.09 g, 0.14 mmol). The yield of
(
3×50 mL). The organic fractions were combined, dried with
3
2
2
1
Na SO , filtered, and concentrated. The residue obtained was
compound 6 was 0.35 g (49%). H NMR (CDCl ), : 7.15 (d, 4 H,
2
4
3
purified by column chromatography (eluent Et O). The first two
mꢀH—C H OMe, J = 5.5 Hz); 6.70 (d, 4 H, oꢀH—C H OMe,
2
6
3
6
3
fractions were collected and concentrated to obtain compound
J = 5.5 Hz); 3.75 (s, 6 H, pꢀCH O—C H —B); 3.63 (br.s, 2 H,
3 6 4
1
1
1
3
a (0.20 g, 35%) and product 3b (0.16 g, 19%), respectively. The
CHcarb). B{ H} NMR (CDCl ), : 7.8 (s, 2 B); –9.2 (d, 2 B);
3
spectral data for compound 3a correspond to those published
–14.1 (d, 4 B); –16.6 (d, 2 B).
earlier.16
9,12ꢀBis(4ꢀfluorophenyl)ꢀ1,2ꢀdicarbaꢀclosoꢀdodecaborane
(7a) and 9ꢀ(4ꢀfluorophenyl)ꢀ12ꢀiodoꢀ1,2ꢀdicarbaꢀclosoꢀdodecaꢀ
borane (7b) were synthesized according to the procedure similar
to that for compounds 3a,b, using Mg (0.56 g, 22.88 mmol),
4ꢀFC H Br (1.58 mL, 2.50 g, 14.30 mmol), 9,12ꢀdiiodoꢀ1,2ꢀ
1
Compound 3b. H NMR (CDCl ), : 3.82 (br.s, 1 H, CHcarb);
3
3
.54 (br.s, 1 H, CH ); 0.94 (m, 3 H, CH CH —B); 0.90 (m, 2 H,
carb 3 2
1
1
1
CH CH —B). B{ H} NMR (CDCl ), : 9.2 (s, 1 B); –7.2
3
2
3
(
d, 2 B); –13.4 (d, 2 B); –14.2 (d+s, 3 B); –15.6 (d, 2 B).
6
4
1
3
1
C{ H} NMR (CDCl ), : 50.3. (br.s, Ccarb); 49.0 (br.s, Ccarb);
dicarbaꢀclosoꢀdodecaborane (1.13 g, 2.86 mmol), CuI (0.03 g,
3
1
3.3 (s, CH CH —B); 11.3 (br.q, CH CH —B).
0.16 mmol), and (Ph P) PdCl (0.09 g, 0.14 mmol). The yield of
3
2
3
2
3
2
2
9
,12ꢀDiphenylꢀ1,2ꢀdicarbaꢀclosoꢀdodecaborane (4). Comꢀ
compound 7a was 0.31 g (33%), for compound 7b 0.22 g (21%).
The spectral data for compound 7a corresponded to those pubꢀ
pound 4 was synthesized according to the procedure similar to
that for compounds 3a,b, using Mg (0.56 g, 22.88 mmol), broꢀ
mobenzene (1.50 mL, 2.25 g, 14.30 mmol), 9,12ꢀdiiodoꢀ1,2ꢀ
dicarbaꢀclosoꢀdodecaborane (1.13 g, 2.86 mmol), CuI (0.03 g,
1
9
lished earlier.
1
Compound 7b. H NMR (CDCl ), : 7.41 (m, 2 H, C H );
3
6
4
7.00 (m, 2 H, C H ); 3.98 (br.s, 1 H, CHcarb); 3.63 (br.s, 1 H,
6
4

7
16
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 3, March, 2015
Anufriev et al.
CHcarb). 11B{ H} NMR (CDCl ), : 6.9 (s, 1 B); –7.7 (d, 2 B);
–
1
Trimethylammonium 5,6ꢀbis(4ꢀmethoxyphenyl)decahydroꢀ
7,8ꢀdicarbaꢀnidoꢀundecaborate (13) was obtained according to
the procedure similar to that for compound 9, using NaOH (0.08 g,
1.92 mmol) and compound 6 (0.34 g, 0.96 mmol). The yield of
3
19
1
13.6 (d, 2 B); –14.5 (d+s, 3 B); –15.4 (d, 2 B). F{ H} NMR
CDCl ), : –114.85 (s, pꢀF—C H —B).
Trimethylammonium 5,6ꢀdibromodecahydroꢀ7,8ꢀdicarbaꢀ
nidoꢀundecaborate (8) was obtained according to the procedure
published earlier.2 H NMR (CD COCD ), : 8.86 (br.s, 1 H,
(
3
6
4
1
compound 13 was 0.21 g (54%). H NMR (CD COCD ), : 7.21
3
3
2 1
(d, 4 H, mꢀH—C H OMe, J = 7.3 Hz); 6.46 (d, 4 H, oꢀH—
3
3
6
3
(
CH ) NH); 3.19 (d, 9 H, (CH ) NH, J = 5.1 Hz); 1.88 (br.s, 2 H,
C H OMe, J = 7.3 Hz); 3.62 (s, 6 H, pꢀCH OC H —B); 3.19
6 3 3 6 4
3
3
3 3
11
1
CHcarb); –2.09 (br.s, 1 H, Hbridge). B{ H} NMR (CD COCD ),

(
(s, 9 H, (CH ) NH); 1.87 (br.s, 2 H, CHcarb); –2.08 (br.s, 1 H,
3 3
3
3
1
1
1
: –10.7 (s+d, 4 B); –19.0 (d, 1 B); –21.9 (d, 2 B); –28.7
Hbridge). B{ H} NMR (CD COCD ), : –6.2 (s, 2 B); –10.1
3 3
d, 1 B); –34.8 (d, 1 B). 13C{ H} NMR (CD COCD ), : 46.7
1
(d, 2 B); –18.6 (d, 1 B); –21.2 (d, 2 B); –30.2 (d, 1 B); –35.9 (d, 1 B).
Trimethylammonium 5,6ꢀbis(4ꢀfluorophenyl)decahydroꢀ7,8ꢀ
dicarbaꢀnidoꢀundecaborate (14) was obtained according to the
procedure similar to that for compound 9, using NaOH (0.04 g,
0.90 mmol) and compound 7 (0.15 g, 0.45 mmol). The yield of
3
3
(s, (CH ) NH); 39.3 (br.q, CHcarb).
3 3
Trimethylammonium 5,6ꢀdimethyldecahydroꢀ7,8ꢀdicarbaꢀ
nidoꢀundecaborate (9). Compound 2 (0.34 g, 2.00 mmol) was
added to a solution of sodium hydroxide NaOH (0.16 g,
4
1
.00 mmol) in 96% aqueous EtOH (20 mL). The mixture was
compound 14 was 0.05 g (29%). H NMR (CD COCD ), : 7.27
3
3
refluxed for 16 h, cooled, filtered, and neutralized with 10%
aqueous solution of hydrochloric acid. A precipitate of sodium
chloride was filtered off, the filtrate was concentrated. The resiꢀ
due was dissolved in water (10 mL), the product was precipitated
(m, 4 H, C H ); 6.61 (m, 4 H, C H ); 3.12 (s, 9 H, (CH ) NH);
1.94 (br.s, 2 H, CHcarb); –2.04 (br.s, 1 H, Hbridge). B{ H}
6 4 6 4 3 3
1
1
1
NMR (CD COCD ), : –6.6 (s, 2 B); –10.0 (d, 2 B); –18.4
3
3
19
(d, 1 B); –21.2 (d, 2 B); –30.2 (d, 1 B); –35.8 (d, 1 B).
F
by an excess of trimethylammonium chloride (Me NHCl) in
(CD COCD ), : –122.00 (s, 2 F, pꢀF—C H —B). MS (EI):
3
3
3
6
4
–
water (10 mL). A white clotted precipitate was filtered off,
found: m/z 321 [M – Me N – H ] ; C H B F ; calculated
3 2 14 17 9 2
1
–
washed, and dried to obtain compound 9 (0.29 g, 65%). H NMR
321 [M – Me N – H ] .
3 2
(
CD COCD ), : 3.24 (s, 9 H, (CH ) NH); 1.53 (br.s, 2 H,
Potassium 9,9´,12,12´ꢀtetrabromooctadecahydroꢀ1,1´,2,2´ꢀ
tetracarbaꢀ3ꢀcommoꢀcobaltaꢀclosoꢀtricosaborate (15). Comꢀ
pound 8 (4.39 g, 12.50 mmol) was added to a freshly prepared
3
3
3 3
CH ); 0.03 (br.s, 6 H, CH —B); –2.46 (br.s, 1 H, Hbridge).
1
carb
3
1
1
B{ H} NMR (CD COCD ), : –7.6 (s, 2 B); –9.9 (d, 2 B);
3
3
–
18.6 (d, 1 B); –21.2 (d, 2 B); –28.9 (d, 1 B); –34.2 (d, 1 B).
40% solution of NaOH in water H O (100 mL). After the compound
2
13
1
C{ H} NMR (CD COCD ), : 46.2 (s, (CH ) NH); 38.5 (br.q,
was completely dissolved and triethylamine ceased to liberate,
CoCl •6H O (5.95 g, 25.00 mmol) was added. The mixture was
3
3
3 3
CHcarb); 2.2 (br.q, CH —B). MS (EI): found: m/z 161 [M –
–
3
2
2
–
–
Me N – H ] ; C H B ; calculated 161 [M – Me N – H ] .
stirred for 4 h, then diluted with diethyl ether (100 mL). The
organic fraction was separated, the aqueous phase was extracted
with diethyl ether (4×50 mL). The organic fractions were combined,
filtered, dried with Na SO , and concentrated. The residue was
3
2
4
15
9
3
2
Trimethylammonium 5,6ꢀdiethyldecahydroꢀ7,8ꢀdicarbaꢀnidoꢀ
undecaborate (10) was obtained according to the procedure simꢀ
ilar to that for compound 9, using NaOH (0.07 g, 1.80 mmol)
and compound 3a (0.18 g, 0.90 mmol). The yield of compound 10
2
4
dissolved in water, the product was precipitated by an excess of
potassium acetate. The precipitate was filtered off, washed with
water, and dried to obtain compound 15 (3.90 g, 92%) as an
1
was 0.11 g (49%). H NMR (CD COCD ), : 3.24 (s, 9 H,
3
3
(
CH ) NH); 1.55 (br.s, 2 H, CH ); 0.83 (m, 6 H, CH CH —B);
3 3 carb 3 2
1
1
1
1
0
.52 (m, 4 H, CH CH —B); –2.54 (br.s, 1 H, Hbridge). B{ H}
orange powder. H NMR (CD COCD ), : 4.23 (br.s, 2 H, CHcarb).
3
2
3
3
1
1
1
NMR (CD COCD ), : –5.4 (s, 2 B); –10.9 (d, 2 B); –18.8 (d, 1 B);
–
B{ H} NMR (CD COCD ), : 6.4 (d, 2 B); 2.9 (d, 2 B); –1.7
(s, 4 B); –6.9 (d, 4 B); –17.1 (d, 2 B); –23.4 (d, 2 B). C{ H}
3
3
3 3
13
1
13
1
21.2 (d, 2 B); –30.4 (d, 1 B); –35.7 (d, 1 B). C{ H} NMR
(
1
CD COCD ), : 45.3 (s, (CH ) NH); 37.3 (br.q, CHcarb);
NMR (CD COCD ), : 46.7 (br.s, CH ). HRMS (ESI): found:
3
3
3 3
3
3
carb
–
–
4.2 (s, CH CH —B); 2.5 (br.q, CH CH —B). MS (MALDI):
m/z 639.9216 [M] ; C H B Br Co; calculated: 639.9232 [M] .
3
2
3
2
4 18 18 4
–
found: m/z 190.4 [M – Me NH] ; C H B ; calculated 190.2
Tetramethylammonium 9,9´,12,12´ꢀtetramethyloctadecaꢀ
hydroꢀ1,1´,2,2´ꢀtetracarbaꢀ3ꢀcommoꢀcobaltaꢀclosoꢀtricosaboꢀ
rate (16). Potassium tertꢀbutoxide (1.39 g, 12.40 mmol) was addꢀ
ed in one portion to a solution of compound 9 (0.27 g, 1.24 mol)
in 1,2ꢀdimethoxyethane (40 mL). The suspension was stirred for
3
6
20 9
–
[
M – Me NH] .
3
Trimethylammonium 5,6ꢀdiphenyldecahydroꢀ7,8ꢀdicarbaꢀ
nidoꢀundecaborate (11) was obtained according to the procedure
similar to that for compound 9, using NaOH (0.10 g, 2.42 mmol)
and compound 4 (0.36 g, 1.21 mmol). The yield of compound 11
was 0.27 g (65%). H NMR (CD COCD ), : 7.33 (m, 4 H,
mꢀH—C H —B); 6.83 (m, 6 H, pꢀ and oꢀH—C H —B); 3.11
30 min. Then, anhydrous CoCl (1.61 g, 1.24 mmol) was added
2
1
in one portion. The solution was refluxed for 20 h. After the
reaction was complete, the mixture was cooled, filtered, and
concentrated. The residue was dissolved in water, the product
3
3
6
4
6
4
(
s, 9 H, (CH ) NH); 1.92 (br.s, 2 H, CHcarb); –2.04 (br.s, 1 H,
3 3
1
1
1
Hbridge). B{ H} NMR (CD COCD ), : –6.2 (s, 2 B); –10.0
was precipitated by an excess of NMe Br in water. The precipiꢀ
3
3
4
(
d, 2 B); –18.4 (d, 1 B); –21.2 (d, 2 B); –30.3 (d, 1 B); –35.9 (d, 1 B).
tate was filtered off, washed, and dried to obtain compound 16
1
Trimethylammonium 5,6ꢀdi(pꢀtolyl)decahydroꢀ7,8ꢀdicarbaꢀ
(0.25 g, 89%) as a brown powder. H NMR (CD COCD ),
3
3
nidoꢀundecaborate (12) was obtained according to the procedure
similar to that for compound 9, using NaOH (0.50 g, 12.48 mmol)
: 3.75 (br.s, 4 H, CH ); 3.47 (br.s, 12 H, N(CH ) ); 0.08 (br.s,
carb 3 4
1
1
1
12 H, CH —B). B{ H} NMR (CD COCD ), : 9.5 (d, 2 B);
3
3
3
and compound 5a (1.35 g, 4.16 mmol). The yield of compound
2.7 (d+s, 6 B); –5.3 (d, 4 B); –17.3 (d, 4 B), –23.6 (d, 2 B).
1
13
1
1
2 was 0.90 g (58%). H NMR (CD COCD ), : 7.22 (d, 4 H,
C{ H} NMR (CD COCD ), : 55.2 (t, N(CH ) ); 45.4 (br.s,
3
3
3 3 3 4
C H , J = 7.6 Hz); 6.68 (d, 4 H, C H ); 3.14 (s, 9 H, (CH ) NH);
CH ); 3.4 (br.q, CH —B). HRMS (ESI): found: m/z 380.3488
carb 3
6
4
6
4
3 3
–
–
2
.11 (s, 6 H, pꢀCH C H —B); 1.89 (br.s, 2 H, CHcarb); –2.06
[M] ; C H B Co; calculated 380.3475 [M] .
3
6
1
4
8 30 18
1
1
(
br.s, 1 H, Hbridge). B{ H} NMR (CD COCD ), : –6.1 (s, 2 B);
Tetramethylammonium 9,9´,12,12´ꢀtetraethyloctadecahyꢀ
droꢀ1,1´,2,2´ꢀtetracarbaꢀ3ꢀcommoꢀcobaltaꢀclosoꢀtricosaborate
(17) was obtained according to the procedure similar to that for
3
3
–
10.0 (d, 2 B); –18.5 (d, 1 B); –21.2 (d, 2 B); –30.2 (d, 1 B);
–
36.0 (d, 1 B).

Tetrasubstituted cobalt bis(dicarbollides)
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 3, March, 2015
717
t
compound 16, using compound 10 (0.07 g, 0.28 mmol), Bu OK
5. J. M. Williams, J. R. Ferraro, R. J. Thorn, K. D. Carlson,
U. Geiser, H. H. Wang, A. M. Kini, M. H. Whangbo, Organꢀ
ic Superconductors (Including Fullerenes: Synthesis, Strucꢀ
ture, Properties, and Theory), Prentice Hall, Englewood
Cliffs, 1992.
6. R. P. Shibaeva, S. S. Khasanov, L. V. Zorina, S. V. Simonov,
Crystallogr. Rep. (Engl. Transl.), 2006, 51, 949 [Kristallogr.,
2006, 51, 1014].
(
0.31 g, 2.80 mmol), and CoCl (0.36 g, 2.80 mmol). The yield of
compound 17 was 0.06 g (84%), a brown powder. H NMR
CD COCD ), : 3.78 (br.s, 4 H, CHcarb); 3.45 (br.s, 12 H,
N(CH ) ); 0.85 (br.s, 12 H, CH CH —B); 0.59 (br.m, 8 H,
CH CH —B). B{ H} NMR (CD COCD ), : 8.2 (d, 2 B); 4.7
s, 4 B); 1.1 (d, 2 B); –6.0 (d, 4 B); –18.2 (d, 4 B); –23.7 (d, 2 B).
C{ H} NMR (CD COCD ), : 56.8 (t, (CH ) N); 47.2 (br.s,
2
1
(
3 3
3
4
3
2
1
1
1
3
2
3
3
(
1
3
1
3
3
3 4
CHcarb); 15.0 (s, CH CH —B); 13.1 (br.q, CH CH —B). HRMS
7. O. N. Kazheva, A. V. Kravchenko, G. G. Alexandrov, I. B.
Sivaev, V. I. Bregadze, I. D. Kosenko, I. A. Lobanova, L. I.
Buravov, V. A. Starodub, O. Dyachenko, Russ. Chem. Bull.
(Int. Ed.), 2014, 63, 1322 [Izv. Akad. Nauk, Ser. Khim.,
2014, 1322].
3
2
3
2
–
(
4
ESI): found: m/z 436.4088 [M] ; C H B Co; calculated
12 38 18
36.4103 [M] .
Potassium 9,9´,12,12´ꢀtetraphenyloctadecahydroꢀ1,1´,2,2´ꢀ
–
tetracarbaꢀ3ꢀcommoꢀcobaltaꢀclosoꢀtricosaborate (18) was obꢀ
tained according to the procedure similar to that for compound
8. O. Kazheva, G. Alexandrov, A. Kravchenko, V. Starodub,
I. Lobanova, I. Sivaev, V. Bregadze, L. Buravov, O. Dyaꢀ
chenko, Solid State Sci., 2008, 10, 1734.
9. O. N. Kazheva, G. G. Alexandrov, A. V. Kravchenko, V. A.
Starodub, I. A. Lobanova, I. B. Sivaev, V. I. Bregadze, L. V.
Titov, L. I. Buravov, O. A. Dyachenko, J. Organomet. Chem.,
2009, 694, 2336.
10. O. N. Kazheva, G. G. Alexandrov, A. V. Kravchenko, V. A.
Starodub, I. B. Sivaev, I. A. Lobanova, V. I. Bregadze, L. I.
Buravov, O. A. Dyachenko, J. Organomet. Chem., 2007,
692, 5033.
1
6, but after evaporation of dimethoxyethane, the residue obꢀ
tained was washed with water. The reaction used compound 11
t
(
(
0.20 g, 0.58 mmol), Bu OK (0.65 g, 5.80 mmol), and CoCl2
0.74 g, 5.80 mmol). The yield of compound 18 was 0.17 g (88%),
a dark brown powder. H NMR (CD COCD ), : 7.37 (br.s,
1
3
3
8
4
H, mꢀH—C H —B); 6.98 (br.s, 12 H, oꢀ and pꢀH—C H —B);
6 4 6 4
1
1
1
.42 (br.s, 4 H, CHcarb). B{ H} NMR (CD COCD ), : 6.9
3
3
(
d, 2 B); 3.7 (s, 4 B); 0.2 (d, 2 B); –5.5 (d, 4 B); –17.2 (d, 4 B);
–
23.9 (d, 2 B).
Potassium 9,9´,12,12´ꢀtetra(pꢀtolyl)octadecahydroꢀ1,1´,
2
,2´ꢀtetracarbaꢀ3ꢀcommoꢀcobaltaꢀclosoꢀtricosaborate (19) was
11. O. N. Kazheva, G. G. Alexandrov, A. V. Kravchenko, I. D.
Kosenko, I. A. Lobanova, I. B. Sivaev, O. A. Filippov, E. S.
Shubin, V. I. Bregadze, V. A. Starodub, L. V. Titov, L. I.
Buravov, O. A. Dyachenko, Inorg. Chem., 2011, 50, 444.
12. O. N. Kazheva, G. G. Aleksandrov, A. V. Kravchenko, V. A.
Starodub, G. G. Zhigareva, I. B. Sivaev, V. I. Bregadze, L. I.
Buravov, L. V. Titov, O. A. D´yachenko, Russ. Chem. Bull.
(Int. Ed.), 2010, 59, 1137 [Izv. Akad. Nauk, Ser. Khim.,
2010, 1115].
obtained according to the procedure similar to that for comꢀ
pound 18, using compound 12 (0.85 g, 2.27 mmol), Bu OK (2.55 g,
t
2
2.70 mmol), and CoCl2 (2.95 g, 22.70 mmol). The yield of
1
compound 19 was 0.54 g (65%), a dark brown powder. H NMR
(
CD COCD ), : 7.24 (m, 8 H, C H ); 6.79 (m, 8 H, C H );
3 3 6 4 6 4
4
.16 (br.s, 4 H, CH ); 2.16 (br.s, 12 H, pꢀCH C H —B).
carb 3 6 4
1
1
1
B{ H} NMR (CD COCD ), : 6.8 (d, 2 B); 3.9 (s, 4 B); 0.2 (d,
3
3
13
1
2
B); –5.5 (d, 4 B); –17.1 (d, 4 B); –23.5 (d, 2 B). C{ H} NMR
(
(
(
6
CD COCD ), : 141.8 (br.q, C—B); 133.7 (s, C—CH ); 133.2
13. V. I. Bregadze, S. V. Timofeev, I. B. Sivaev, I. A. Lobanova,
Russ. Chem. Rev., 2004, 73, 433.
14. L. Matel, F. Macašek, P. Rajec, S, Heшmanek, J. Plešek,
Polyhedron, 1982, 1, 511.
3
3
3
s, CH); 126.9 (s, CH); 47.3 (br.s, CH ); 20.3 (s, CH ). HRMS
carb
3
–
ESI): found: m/z 684.4742 [M] ; C H B Co; calculated
3
2
46 18
–
84.4742 [M] .
1
1
1
5. H. D. Smith, T. A. Knowles, H. Schroeder, Inorg. Chem.,
965, 4, 107.
6. Z. Zheng, W. Jiang, A. A. Zinn, C. B. Knobler, M. F. Hawꢀ
thorne, Inorg. Chem., 1995, 34, 2095.
7. M. J. Bayer, A. Herzog, M. Diaz, G. A. Harakas, H. Lee,
C. B. Knobler, M. F. Hawthorne, Chem. Eur. J., 2003,
1
This work was financially supported by the Russian
Foundation for Basic Research (Project Nos 13ꢀ03ꢀ00581
and 14ꢀ03ꢀ00925).
References
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1
1
8. M. A. Fox, K. Wade, J. Mater. Chem., 2002, 12, 1301.
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. (a) M. F. Hawthorne, T. D. Andrews, Chem. Commun., 1964,
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2
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0. G. Laurent, S.ꢀJ. Laurent, Tetrahedron Lett., 2006, 47, 5705.
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3
2
2. A. R. Siedle, G. M. Bodner, L. J. Todd, J. Organomet. Chem.,
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999, 64, 783.
1
971, 33, 137.
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. R. N. Grimes, Carboranes, Academic Press, London, 2011.
in revised form January 13, 2015