Reaction of germanium tetrachloride with chloro(phenyl)silanes in the presence of aluminum chloride

Article abstract of DOI:10.1007/s11176-005-0336-5

The effect of the quantity of aluminum chloride on the direction and depth of reaction of germanium tetrachloride with chloro(phenyl)silanes of the general formula Ph_nSiCl_4-n (n = 1 - 3) was studied to show that radical exchange between germanium and silicon is initiated only if the mixture contains no less than 2.5-5 wt % of aluminum chloride. With trichloro(phenyl)silane, the radical exchange is initiated at 5 wt % of aluminum chloride and results in exclusive formation of trichloro(phenyl)germane. The reactions of GeCl₄ with dichlorodiphenylsilane and chlorotriphenylsilane in the presence of 2.5-7.5 wt % of aluminum chloride give dichlorodiphenylgermane as the major product, and at AlCl₃ concentrations of above 10 wt % the major product becomes to be trichloro(phenyl)germane.

Full text of DOI:10.1007/s11176-005-0336-5

Russian Journal of General Chemistry, Vol. 75, No. 6, 2005, pp. 867 869. Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 6, 2005,
pp. 920 922.
Original Russian Text Copyright
2005 by Zhun’, Sbitneva, Chernyshev.
Reaction of Germanium Tetrachloride
with Chloro(phenyl)silanes in the Presence
of Aluminum Chloride
V. I. Zhun’, I. V. Sbitneva, and E. A. Chernyshev
State Research Institute of Chemistry and Technology of Organoelement Compounds,
Russian State Research Center, Moscow, Russia
Received February 10, 2004
Abstract The effect of the quantity of aluminum chloride on the direction and depth of reaction of
germanium tetrachloride with chloro(phenyl)silanes of the general formula PhnSiCl4 (n = 1 3) was studied
n
to show that radical exchange between germanium and silicon is initiated only if the mixture contains no
less than 2.5 5 wt% of aluminum chloride. With trichloro(phenyl)silane, the radical exchange is initiated at
5 wt% of aluminum chloride and results in exclusive formation of trichloro(phenyl)germane. The reactions of
GeCl4 with dichlorodiphenylsilane and chlorotriphenylsilane in the presence of 2.5 7.5 wt% of aluminum
chloride give dichlorodiphenylgermane as the major product, and at AlCl3 concentrations of above 10 wt%
the major product becomes to be trichloro(phenyl)germane.
We previously observed exchange of phenyl ra-
5% AlCl3
dicals for chlorine in a mixture of dichloro(methyl)-
(phenyl)silane and germanium chloride, heated in the
presence of 30 40 wt% of aluminum chloride [1].
More recently this reaction was studied in detail on an
example of chloro(methyl)(phenyl)silanes [2, 3], but,
like in [1], it was performed in the presence of 30
40 wt% of aluminum chloride. Proceeding with this
research, we studied in the present work the effect of
the quantity of aluminum chloride on the direction
and depth of reaction of germanium tetrachloride with
PhSiCl3 + GeCl4
PhGeCl3 + SiCl4.
The reactions of GeCl4 with dichlorodiphenylsilane
and chlorotriphenylsilane in the presence of 2.5
7.5 wt% of aluminum chloride afforded dichlorodi-
phenylgermane as the major product, while at AlCl3
concentrations of above 10 wt% the major product
became to be trichloro(phenyl)germane.
2.5 7.5% AlCl3
PhnSiCl4 n + GeCl4
PhnSiCl5 n + Ph2GeCl2,
Phn 1SiCl5 n + PhGeCl3.
chloro(phenyl)silanes PhnSiCl4 (n = 1 3), as well
10 30% AlCl3
n
PhnSiCl4 n + GeCl4
as the possibility of radical exchange not only in the
presence aluminum chloride, but also in the presence
of other metal halides possessing Lewis acid properties
(Table 1).
Obviously, as the fraction of aluminum chloride in
the reaction mixture is increased, dichloro(diphenyl)-
Table 1. Reaction of Ph2SiCl2 with GeCl4 (1: 1) in the
presence of various metal halides
It was found that no reaction occurred in the
presence of antimony trichloride, tin tetrachloride, or
titanium tetrachloride, whereas the reaction with
chloro(phenyl)silanes in the presence of boron tri-
fluoride etherate gave fluoro(phenyl)silanes.
Composition of the reaction
Catalyst
(%)
mixture, %
T,
C
At the same time, chlorine at germanium in GeCl4
exchanged for phenyl at silicon as the concentration
of AlCl3 was decreased to 5 wt% in the reaction with
trichloro(phenyl)silane and to 2.5 wt% in the reac-
tions with dichloro(phenyl)- and chlorotriphenyl-
silanes. The reaction with trichloro(phenyl)silane
resulted in exclusive formation of trichloro(phenyl)-
germane.
PhSiCl3 Ph2SiCl2 Ph2SiF2 GeCl4
SbCl3 (30) 100 110
4.1
51.2
46.6
44.6
38.7
38.7
SbCl3 (50) 125 135 14.7
BF3 Et2O 125 135
(50)
15.0
TiCl4 (50)
135
No reaction
1070-3632/05/7506-0867 2005 Pleiades Publishing, Inc.

868
ZHUN’ et al.
Table 2. Reaction of PhnSiCln with GeCl4 in the presence of AlCl3
Composition of the reaction mixture, %
PhSiCl3 Ph2SiCl2 Ph3SiCl PhGeCl3 Ph2GeCl2 GeCl4 SiCl4
No reaction
PhnSiCl4 n : GeCl4
ratio
Catalyst
(%)
PhnSiCl4 n
T,
C
PhSiCl3
PhSiCl3
PhSiCl3
PhSiCl3
PhSiCl3
PhSiCl3
PhSiCl3
PhSiCl3
Ph2SiCl2
Ph2SiCl2
Ph2SiCl2
Ph2SiCl2
Ph2GeCl2
Ph2SiCl2
Ph2SiCl2
Ph2GeCl2
Ph2SiCl2
Ph3SiCl
Ph3SiCl
Ph3SiCl
Ph3SiCl
Ph3SiCl
1: 1
1: 1
1: 1
1: 1
1: 1
2: 1
2: 1
2: 1
1: 1
AlCl3 (2.5) 115 125
AlCl3 (5) 115 125
AlCl3 (7.5) 115 125
AlCl3 (10) 115 125
AlCl3 (20) 115 125
AlCl3 (10) 145
AlCl3 (15) 150
AlCl3 (20) 155
AlCl3 (2.5) 150
AlCl3 (2.5) 130 135
AlCl3 (3.5) 150
AlCl3 (5)
AlCl3 (5)
AlCl3 (5)
AlCl3 (10) 120 150
AlCl3 (10) 100
AlCl3 (20) 110
AlCl3 (2.5) 150
AlCl3 (5)
AlCl3 (5)
AlCl3 (7.5) 140
AlCl3 (7.5) 145
45.2
39.8
40.4
16.9
49.3
47.1
36.1
54.0
44.3
51.8
29.9
2.8
4.9
46.1
49.8
38.3
36.5
28.5
9.0
0.2
25.5
40.4
23.2
4.8
46.3
44.9
8.9
27.9
7.5
10.9
32.6
0.2
13.7
0.9
5.7
10.4
4.5
5.4
4.9
3.5
2.9
19.7
1.0
19.3
0.1
16.0
22.5
2.8
2: 1
1: 1
1: 1
18.1
6.3
135 145
70 80
110
1.1
4.7
16.7
55.8
1.35: 1
2: 1
1: 1
1.35: 1
1: 1
20.1
27.6
2.8
58.9
41.7
1.8
0.5
6.3
10.9
43.2
0.8
73.4
17.3
0.3
49.1
27.9
5.5
1: 1
1: 1
1: 1
1: 1
No reaction
145
150 155
5.4
35.5
25.4
80.1
49.3
2.0
14.5
12.8
3.8
1.6
26.7
37.9
0.8
37.6
46.4
2.8
2.1
Excess GeCl4
(1: 1.5)
1: 1
11.5
17.6
1.0
Ph3SiCl
Ph3SiCl
Ph3SiCl
Ph3SiCl
Ph3SiCl
Ph3SiCl
AlCl3 (10) 135
AlCl3 (10) 135
AlCl3 (10) 150 155
AlCl3 (20) 125
AlCl3 (30) 135
AlCl3 (7.5) 140 145
53.8
13.5
15.5
67.3
52.6
1.2
7.5
13.8
26.6
18.2
14.9
0.5
0.8
4.8
2: 1
3: 1
1: 1
1: 1
54.9
53.9
28.7
40.0
1.9
4.7
2.4
0.7
0.9
No GeCl4
added
With GeCl4
added (1: 1)
29.8
70.2
0.3
Ph3SiCla
AlCl3 (7.5) 140
39.2
8.6
47.1
a
GeCl was added to preliminarily heated mixture of Ph SiCl with AlCl .
4
3
3
germane enter reaction with unreacred germanium
tetrachloride to form trichloro(phenyl)germane.
Evidence for this suggestion was obtained in a special
experiment (Table 2).
packing 5% SE-30 on Chromasorb G-AW-DMCS
(0.15 0.18 mm); the oven temperature was prog-
rammed from 50 to 290 C at a rate of 12 degmin .
1
Injector temperature 320 C, thermal conductivity
detector, detector temperature 300 C, detector current
10% AlCl3
1
Ph2GeCl2 + GeCl4
2PhGeCl3.
90 mA. Carrier gas helium, rate 30 mlmin .
EXPERIMENTAL
All experiments were performed with commercial
Reaction of chloro(phenyl)silanes with tetra-
chlorogermane. A mixture of chloro(phenyl)silane,
tetrachlorogermane, and aluminum chloride was
heated at 100 C for 3 h and then cooled and analyzed
by GLC. The calculated product yields are given in
Tables 1 and 2.
reagents.
Reaction products were analyzed by GLC on an
LKhM-80 chromatograph: metallic column 1000.3 mm,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 6 2005

REACTION OF GERMANIUM TETRACHLORIDE
869
REFERENCES
2. Motsarev, G.V., Chernyshev, E.A., Rozenberg, V.R.,
Inshakova, V.T., and Zetkin, V.I., Zh. Obshch. Khim.,
1983, vol. 53, no. 5, p. 1111.
3. Lakhtin, V.G., Yakovleva, M.V., and Chernyshev, E.A.,
Available from VINITI, 2002, Moscow, no. 2071-V2002.
1. Chernyshev, E.A., Kurek, M.E., and Polivanov, A.N.,
USSR Inventor’s Certificate no. 316693, 1970, Byull.
Izobret., 1971, no. 30.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 6 2005