528
AVDEEVA et al.
complex [Au (Ph P) ](NO ) [23]. Other reducing
(а)
9
3
8
3 3
3+
agents are also useful for preparing [Au (Ph P) ] , for
9
3
8
example, the titanium complex [Ti(
η
ꢀC H Me)2] [24].
5 5
In our case, the reducing agent is likely to be the initial
2
−
closoꢀdodecaborate anion B H .
1
2
12
To summarize, we may say that having studied the
2
−
behavior of the closoꢀdodecaborate anion B H in
1
2
12
reaction with Au(Ph P)Cl, we found a number of feaꢀ
3
tures of the complexing process. We have found that
+
+
Cat B H salts of organic cations (Cat = Ph P ,
2
12 12
4
Bu N+) do not react with Au(Ph P)Cl in acetonitrile,
(b)
4
3
whereas the use of [Ag B H12] as the precursor closo
ꢀ
2
12
dodecaborate and variation of the reagent ratio proꢀ
duce fundamentally different products. The equimolar
ratio of [Ag B H12] to Au(Ph P)Cl yields a silver(I)
Au(5)
2
12
3
Au(2)
complex that is the first example where the closo
ꢀ
Au(3)
Au(4)
Au(4A)
Au(3A)
dodecaborate anion is coordinated to silver(I) atoms
Au(1)
in the face coordination. The reaction of [Ag B H12]
2
12
with an excess of Au(Ph P)Cl generates ideal condiꢀ
3
Au(5A)
3–
3+
tions for preparing [В Н ] and [Au (Ph P) ]
,
24
23
9
3
8
Au(2A)
whereas the preparation of the aforementioned cation
and anion individually requires applying more severe
conditions. Both complexes contain gold atoms,
which are however not linked to the cluster boron
anion.
Fig. 3. Crystal structure of compound II: (a) [В24Н23]3–
3+
(
anionic part) and (b) [Au (Ph P) ] (cationic part).
9 3 8
ACKNOWLEDGMENTS
respectively in match with theoretical calculations
The authors are grateful to Xꢀray Structure
Research Center of the Institute of Organoelement
Compounds, Russian Academy of Sciences, for carryꢀ
ing out the diffraction experiment on a crystal of comꢀ
plex II. This work was supported by the Program for
Support of Leading Scientific Schools (grant
no. NShꢀ1518.2008.3) and the Russian Foundation
for Basic Research (project no. 07ꢀ03ꢀ00637).
3
−
[
19]. The existence of the trianion В Н in complex
24 23
11
II is unambiguously identified by B NMR and IR
spectroscopy [9].
3
+
Compounds of the cation [Au (Ph P) ] and anion
9
3
8
3–
[
В Н ] with other counterions are known in the litꢀ
24 23
2
−
erature. The oxidation of B H to yield trianion
В Н ] was described as early as in 1969 [20];
1
2
12
3–
[
24 23
Na [В Н ] was obtained by electrolysis of a solution
3
24 23
REFERENCES
of Na B H in acetonitrile at 1.5 V:
2
12 12
1
.
The Chemistry of Inorganic Hydrides. Collected Works
Ed. by N. T. Kuznetsov (Nauka, Moscow, 1990) [in
Russian].
,
2
12
−
3−
+
2
B H
В Н + Н + 2e.
24 23
1
2
Based on the data of elemental analysis and IR and
NMR spectroscopy, a link by a bridging hydrogen
2. N. Chaozhou, M. Yilin, and S. Cuifang, Acta Chim.
Sin. 43 (5), 411 (1985).
3
−
atom between the two В Н icosahedra in В Н was
2
4
23
12 11
3
. V. V. Drozdova, E. A. Malinina, N. T. Kuznetsov, et al.,
Zh. Neorg. Khim. 51 (11), 1832 (2006) [Russ. J. Inorg.
Chem. 51 (11), (2006)].
suggested [20].
Later [21], the Xꢀray diffraction structure of the triꢀ
anion [В Н ] was determined. The angle BHB'
between the icosahedra was 128.2 , whereas in comꢀ
plex II, the B–H–B' bridge is strictly linear (in terms
3–
24
23
4. E. A. Malinina, V. V. Drozdova, N. T. Kuznetsov, et al.,
Zh. Neorg. Khim. 53 (7), 1105 (2008) [Russ. J. Inorg.
Chem. 53 (7), (2008)].
°
of symmetry).
5. O. Volkov, Ch. Hu, and P. Paetzold, Z. Anorg. Allg.
Chem. 631 (6–7), 1107 (2005).
Polynuclear gold clusters with triphenylphosphine
and its derivatives are described in [22]. Nonanuclear
gold clusters are mostly prepared by the reduction of
mononuclear gold(I) complexes. Specifically, the
reduction of Au(Ph P)NO by NaBH4 produced the
6. V. V. Drozdova, E. A. Malinina, N. T. Kuznetsov, et al.,
Zh. Neorg. Khim. 53 (2), 238 (2008) [Russ. J. Inorg.
Chem. 53 (2), (2008)].
3
3
7. T. Chaper and W. Preetz, Chem. Ber. 130, 405 (1997).
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 56 No. 4 2011