PdCl2 and NiCl2-catalyzed hydrogen-halogen exchange for the convenient preparation of bromo- and iodosilanes and germanes

Article abstract of DOI:10.1016/S0022-328X(02)02147-2

Bromination and iodination of hydrosilanes and germanes were studied. Treatment of hydrosilanes with an excess of ethyl, propyl, or allyl bromide in the presence of a catalytic amount of PdCl₂ or NiCl₂ gave bromosilanes in good to high yield by hydrogen-halogen exchange. By using methyl, propyl, or allyl iodide as the iodine source, similar iodination of hydrosilanes was readily performed. Halogenation of hydrogermanes also proceeded by similar treatment.

Full text of DOI:10.1016/S0022-328X(02)02147-2

Journal of Organometallic Chemistry 667 (2003) 90Á95
/
www.elsevier.com/locate/jorganchem
PdCl2 and NiCl2-catalyzed hydrogenÁ
/
halogen exchange for the
convenient preparation of bromo- and iodosilanes and germanes
Arihiro Iwata a, Yutaka Toyoshima a, Tsuyoshi Hayashida a, Takahiko Ochi a,
Atsutaka Kunai a,*, Joji Ohshita b
a Department of Applied Chemistry, Graduate School of Engineering, Hiroshima University, Higashi-Hiroshima 739-8527, Japan
b Institute for Fundamental Research of Organic Chemistry, Kyushu University, Fukuoka 812-8581, Japan
Received 13 August 2002; received in revised form 20 November 2002; accepted 22 November 2002
Abstract
Bromination and iodination of hydrosilanes and germanes were studied. Treatment of hydrosilanes with an excess of ethyl,
propyl, or allyl bromide in the presence of a catalytic amount of PdCl2 or NiCl2 gave bromosilanes in good to high yield by
hydrogenÁhalogen exchange. By using methyl, propyl, or allyl iodide as the iodine source, similar iodination of hydrosilanes was
/
readily performed. Halogenation of hydrogermanes also proceeded by similar treatment.
# 2002 Elsevier Science B.V. All rights reserved.
Keywords: Bromosilane; Iodosilane; Bromogermane; Iodogermane
1. Introduction
Lewis-acid also produce an MÃ
/
X bond. Cleavage of an
alkyl-Ge bond with X2 and Lewis-acid-catalyzed redis-
Halosilanes and germanes are of important reagents
as the building units for a variety of organosilicon and
germanium compounds. In addition, bromo- and iodo-
silanes exhibit high Lewis-acidity to permit the interac-
tribution reactions of R4Ge and GeBr4 are also often
used for the formation of a GeÃ
/
X bond. However, most
of these methods involve the use or by-production of
unpleasant HX or X2. Furthermore, traces of HX and
X2 may contaminate the resulting halosilanes and
germanes.
Previously, we have found that the reactions of mono-
and dihydrosilanes with alkyl iodides in the presence of
a catalytic amount of PdCl2 afford mono- and diiodo-
silanes in high yield [7]. We have also reported the CuI-
catalyzed bromination of hydrosilanes with CuBr2 [8], in
tion with CÃ
/
O and CÄ/O bonds, unlike fluoro- and
chlorosilanes [1]. Examples include the reactions of
ethers and esters with iodo- and bromosilanes, which
afford silyl ethers and esters, respectively, together with
halides arising from CÃ/O bond cleavage, in good yield
[2,3]. It is also known that aldehydes react with
iodosilanes to give silyl a-iodoalkyl ether, by iodosilyla-
tion of the carbonyl bond [4,5].
which an SiÃ
/
H bond is replaced with an SiÃ/Br group
Conventional methods to prepare bromo- and iodo-
with the use of two equivalents of CuBr2. However,
there may be a limitation that this method can not be
applied to the preparation of tribromosilanes, and
treatment of trihydrosilanes with six equivalents of the
reagent gives dibromohydrosilanes as the sole isolable
products. In this paper, we report a versatile method to
prepare bromo- and iodosilanes, including tribromo-
and triiodosilanes from PdCl2- or NiCl2-catalyzed
silanes [1] and germanes [6] involve the cleavage of MÃ
M, MÃH, MÁallyl, and MÁaryl bonds (MꢀSi, Ge)
with X2 (XꢀBr, I), reactions of MÃH with HX (Xꢀ
Br, I) and NBS, and halogen exchange of MÃCl with
inorganic halides. Reactions of an MÃOÃM bond with
HX in the presence (MꢀSi) or absence (MꢀGe) of a
/
/
/
/
/
/
/
/
/
/
/
/
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hydrogenÁhalogen exchange reactions of hydrosilanes
with alkyl bromides and iodides, respectively. Similar
halogenation of hydrogermanes is also described.
/
* Corresponding author. Tel.: ꢁ
5494.
E-mail address: akunai@hiroshima-u.ac.jp (A. Kunai).
/
81-824-24-7727; fax: ꢁ81-824-24-
/
0022-328X/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0022-328X(02)02147-2

A. Iwata et al. / Journal of Organometallic Chemistry 667 (2003) 90Á
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2. Results and discussion
2.1. Bromination of hydrosilanes
Scheme 1.
The reactions of hydrosilanes with alkyl or allyl
bromides in the presence of a catalytic amount of
PdCl2 or NiCl2 proceeded with the liberation of alkanes
to give brominated products in good to high yields
(Table 1 and Scheme 1). As can be seen in Table 1, the
reactions proceeded more rapidly when allyl bromide,
rather than ethyl and propyl bromide, was used as the
halide. Typically, PdCl2-catalyzed bromination of
PhMe2SiH with EtBr or PrBr completed by refluxing
the mixture without solvent for 12 h (runs 2 and 3),
while with allyl bromide PhMe2SiH was wholly con-
sumed within 1 h (run 4). Similar NiCl2-catalyzed
bromination of PhMe2SiH with allyl bromide proceeded
less rapidly and required the use of a larger amount of
the catalyst and a longer reaction period to complete the
conversion (run 5), as compared with the PdCl2-
catalyzed one (run 4). Lower activity of NiCl2-catalyst
relative to PdCl2 is evident for tribromination of
PhSiH3, in which the Nickel-catalyst was deactivated
during the reaction progress and continuous addition of
the catalyst into the reaction mixture was necessary to
promote further the reaction (run 16). In contrast to
this, PhSiBr3 was obtained in 88% yield from PhSiH3
with only 1 mol.% of the PdCl2-catalyst (run 15).
were obtained (runs 9, 10, and 13), a few unidentified
products in low yields in addition to the partially
brominated products, were found to be formed by the
GLC analysis of the reaction mixtures.
2.2. Iodination of hydrosilanes
Previously, we have reported that mono- and dihy-
drosilanes readily undergo periodination of SiÃ
/H bonds
when they are treated with alkyl iodides in the presence
of a catalytic amount of PdCl2 [7]. As shown in Table 2,
NiCl2-catalyzed reactions also could be used for the
synthesis of iodosilanes. Interestingly, the NiCl2-cata-
lyzed reaction of Et2SiH2 with MeI proceeded more
selectively (run 3), as compared with the reaction with
the PdCl2 catalyst reported previously (run 1). Thus, the
PdCl2-catalyzed reaction gave Et2SiI2 and Et2MeSiI in
37% and 20% yields (run 1, previous result), respectively,
while with NiCl2 as the catalyst, the reaction gave
Et2SiI2 almost selectively (60% yield), with an only 4%
yield of Et2MeSiI. The use of i-PrI as the halide led to
even more selective formation of the simply halogenated
products (runs 4, 6, and 7), as reported previously (run
2) [7]. Triiodosilanes HexSiI3 and PhSiI3 also could be
obtained from the corresponding trihydrosilanes by this
method (runs 8 and 9).
Although partially brominated products were found
to be formed by GCÁMS analyses of the reaction
/
mixtures in low yields in the bromination of di- and
trihydrosilanes, they were readily separated from the
perbrominated products by fractional distillation. In the
reactions, from which rather low yields of bromosilanes
Table 1
Bromination of hydrosilanes
a
b
Run
Hydrosilane (amt/mmol)
Halide (eq)
Catalyst (mol.%)
Temp/8C (time/h)
Product (yield/%)
1
2
Et3SiH (64.2)
PhMe2SiH (15.5)
(31.3)
allylBr (1.8)
EtBr (2.1)
PdCl2 (1)
PdCl2 (1)
PdCl2 (1)
PdCl2 (1)
NiCl2 (6)
PdCl2 (1)
PdCl2 (1)
NiCl2 (5)
PdCl2 (2)
PdCl2 (1)
NiCl2 (2)
PdCl2 (1)
NiCl2 (3)
NiCl2 (2)
PdCl2 (1)
80 (12)
50 (12)
80 (12)
80 (1)
Et3SiBr (90)
PhMe2SiBr (88)
PhMe2SiBr (94)
PhMe2SiBr (88)
PhMe2SiBr (91)
Ph2MeSiBr (76)
Ph2MeSiBr (91)
Ph2MeSiBr (78)
Et2SiBr2 (61)
3
n-PrBr (1.4)
allylBr (1.6)
allylBr (1.8)
EtBr (2.6)
4
(10.9)
(13.2)
5
80 (16)
50 (36)
80 (1)
6
Ph2MeSiH (13.6)
(7.8)
(10.0)
7
allylBr (1.5)
allylBr (1.6)
EtBr (3.0)
8
80 (24)
50 (72)
80 (20)
80 (24)
80 (36)
50 (48)
80 (50)
80 (60)
80 (90)
9
Et2SiH2 (36.1)
(40.0)
(24.0)
10
11
12
13
14
15
16
allylBr (2.3)
allylBr (2.9)
allylBr (3.5)
EtBr (3.0)
Et2SiBr2 (37)
Et2SiBr2 (85)
PhMeSiH2 (18.0)
(39.2)
(18.0)
PhMeSiBr2 (79)
PhMeSiBr2 (59)
PhMeSiBr2 (80)
PhSiBr3 (88)
allylBr (3.5)
allylBr (4.0)
allylBr (2.8)
PhSiH3 (17.0)
(24.1)
c
NiCl2 (11)
PhSiBr3 (65)
a
b
c
Bath temperature.
Isolated yield.
NiCl2 was added in eight portions in every 10Á12 h.
/

92
A. Iwata et al. / Journal of Organometallic Chemistry 667 (2003) 90Á
/95
Table 2
Iodination of hydrosilanes
a
b
Run Hydrosilane (amt/mmol)
Halide (eq)
Catalyst (mol.%)
Temp/8C (time/h)
Product (yield/%)
c
1
2
3
4
5
6
7
8
9
Et2SiH2 (33.8)
(56.1)
(36.5)
MeI (3.0)
i-PrI (2.0)
MeI (3.3)
i-PrI (3.0)
MeI (2.6)
i-PrI (2.6)
i-PrI (2.4)
i-PrI (4.5)
i-PrI (4.5)
PdCl2 (4)
PdCl2 (1)
NiCl2 (6)
NiCl2 (3)
PdCl2 (1)
PdCl2 (1)
NiCl2 (1)
PdCl2 (2)
PdCl2 (1)
60 (24)
70 (24)
60 (40)
100 (18)
60 (72)
100 (12)
100 (18)
90 (48)
90 (40)
Et2SiI2 (37), Et2MeSiI (20)
Et2SiI2 (74)
c
Et2SiI2 (60), Et2MeSiI (4)
Et2SiI2 (52)
(10.0)
PhMeSiH2 (46.3)
(37.7)
(41.9)
PhMeSiI2 (48), PhMe2SiI (22)
PhMeSiI2 (87)
PhMeSiI2 (87)
HexSiH3 (15.0)
PhSiH3 (18.5)
HexSiI3 (86)
PhSiI3 (80)
a
Bath temperature.
Isolated yield.
Ref. [7].
b
c
2.3. Halogenation of hydrogermanes
60 8C for 70 h and the resulting mixture was analyzed
by GCÁMS, Hex3GeI was found to be formed only in
/
It has been reported that heating hydrogermanes with
alkyl halides at 80Á90 8C for several hours leads to the
25% yield, together with the starting Hex3GeH remain-
ing in 70% yield. On the other hand, similar reaction
with allyl iodide produced Hex3GeI in 84% yield (run 9).
Dihydrogermanes were readily converted to dibromo-
germanes (runs 5 and 6), while a longer reaction period
was required to complete the tribromination of Hex-
GeH3 and the product HexGeBr3 was isolated in rather
low yield (58%, run 7). On the contrary, the reaction of
HexGeH3 with allyl iodide proceeded smoothly to
afford HexGeI3 in 87% yield (run 13). The use of NiCl2
as the catalyst did not obviously accelerate the halo-
genation of hydrogermanes.
In the present halogenation of hydrosilanes and
germanes, the formation of fine black precipitates was
observed, immediately after the contact of the reactants
with the catalysts. At the same time, the corresponding
chlorosilanes or germanes were found to be formed by
/
formation of halogermanes in high yield [12]. In contrast
to this, PdCl2-catalyzed halogenation of hydrogermanes
with allyl halides proceeded even at room temperature
(Table 3). In these reactions, allyl halide must be used as
the halogen source. Indeed, no reactions occurred when
Hex3GeH was treated with EtBr at 50 8C in the
presence of the PdCl2 catalyst, while Hex3GeBr was
obtained in 80% yield by the reaction with allyl bromide
at room temperature (run 1). Benzyl bromide could be
also used for the preparation of Hex3GeBr from
Hex3GeH (run 3). When Hex3GeH was treated with
an excess of MeI and a catalytic amount of PdCl2 at
GCÁMS analysis of the reaction mixtures. This seems to
/
Table 3
PdCl2-catalyzed halogenation of hydrogermanes at room temperaturea
indicate that the actual active species in these reactions
were Pd(0) and Ni(0) metals, respectively, formed from
the reduction of the chlorides with hydrosilanes or
germanes, although we have obtained no clear evidences
concerning the reaction mechanism. Presumably, the
b
Run Hydrosilane
(amt/mmol)
Halide (eq)
time/h Product (yield/%)
1
2
Et3GeH (1.5)
allylBr (1.7)
3
3
Et3GeBr (84)
Hex3GeBr (80)
Hex3GeBr (88)
Ph3GeBr (72)
Hex2GeBr2 (92)
Ph2GeBr2 (81)
HexGeBr3 (58)
Et3GeI (83)
homolytic MÃ
/
H (MꢀSi or Ge) bond cleavage occurred
/
Hex3GeH (1.0) allylBr (2.3)
PhCH2Br (1.5)
3
6
on the metal surface and the resulting silyl or germyl
radicals abstract the halogen atom from the halides.
Metathesis type reactions on the metal surface also
would be involved.
4
Ph3GeH (1.0)
allylBr (1.5)
3
5
Hex2GeH2 (2.8) allylBr (3.0)
Ph2GeH2 (1.9) allylBr (3.0)
HexGeH3 (3.1) allylBr (3.6)
6
6
4
7
53
6
8
Et3GeH (5.0)
Hex3GeH (5.0) allylI (1.5)
Ph3GeH (5.0) allylI (1.5)
allylI (1.5)
9
12
12
3
Hex3GeI (84)
Ph3GeI (98)
c
10
11
12
13
Hex2GeH2 (3.0) allylI (3.0)
Ph2GeH2 (3.0) allylI (3.0)
HexGeH3 (3.1) allylI (4.1)
Hex2GeI2 (80)
Ph2GeI2 (75)
HexGeI3 (87)
5
12
3. Conclusions
a
b
c
In conclusion, we studied the PdCl2- and NiCl2-
1Á
Isolated yield.
2 ml of benzene was added to the mixture after 6 h reaction, in
/
3 mol.% of PdCl2 was used.
catalyzed hydrogenÁhalogen exchange of hydrosilanes
/
and germanes with alkyl halides. The reactions pro-
ceeded more readily with the PdCl2 catalyst, but more
order to dissolve the product Ph3GeI.

A. Iwata et al. / Journal of Organometallic Chemistry 667 (2003) 90Á
/95
93
economic NiCl2 also can be used as the catalyst for the
preparation of halosilanes. This provides a versatile
synthetic method leading to a variety of bromo- and
iodosilanes and germanes, which would be expected as
useful synthetic tools for various organosilicon and
germanium compounds. However, we have not yet
succeeded in performing the selective halogenation
leading to halohydrosilanes and germanes by the present
method, the metal-catalyzed exchange reaction. All
attempts to prepare partially halogenated products
selectively from dihydro- and trihydrosilanes and ger-
manes were unsuccessful. In fact, the GLC-trace of the
reaction progress indicated that the perhalogenated
products were formed, together with the partially
halogenated ones, even at the early stage of the
reactions. Studies to optimize the reaction conditions
for the selective halogenation are in progress.
Data for PhMe2SiBr: b.p. 95Á
/
96 8C/17 mmHg; MS
m/z 214 [Mꢁ], 199 [Mꢁ Á
/
Me], 137 [Mꢁ Á
Ph], 135
/
1
[Mꢁ Á
/
Br]; H-NMR (in CDCl3) d 0.84 (s, 6H), 7.36Á
/
7.65 (m, 5H); 13C-NMR (in CDCl3) d 2.86, 128.09,
128.32, 130.58, 133.19; 29Si-NMR (in CDCl3) d 16.78.
Anal. Found: C, 44.66; H, 5.41. Calc. for C8H11BrSi: C,
44.66; H, 5.15%.
Data for Ph2MeSiBr: b.p. 97Á
/
99 8C/1 mmHg; MS m/
Ph], 197 [Mꢁ Á
7.65 (m,
z 276 [Mꢁ], 261 [Mꢁ ÁMe], 199 [Mꢁ Á
/
/
/
1
Br]; H-NMR (in CDCl3) d 1.10 (s, 3H), 7.31Á
/
10H); 13C-NMR (in CDCl3) d 1.78, 128.10, 128.25,
130.58, 134.27; 29Si-NMR (in CDCl3) d 8.05. Anal.
Found: C, 56.79; H, 4.80. Calc. for C13H13BrSi: C,
56.32; H, 4.73%.
Data for Et2SiBr2: b.p. 42Á
166.2Á
166.3 8C/744 mmHg [9]); MS m/z 244 [Mꢁ], 215
[Mꢁ Á
Et]; H-NMR (in CDCl3) d 1.09 (t, 6H, Jꢀ
Hz), 1.27 (q, 4H, Jꢀ
8.1 Hz); 13C-NMR (in CDCl3) d
1.78, 6.90, 14.30.
Data for MePhSiBr2: b.p. 66Á
105 8C/12 mmHg [13]); MS m/z 278 [Mꢁ], 263 [Mꢁ Á
Me], 201 [Mꢁ ÁPh], 199 [Mꢁ ÁBr]; 1H-NMR (in CDCl3)
d 1.33 (s, 3H), 7.46Á7.49 (m, 3H), 7.73Á7.77 (m, 2H);
/
47 8C/11 mmHg (Lit.
/
1
/
/8.1
/
4. Experimental
/
68 8C/1 mmHg (Lit.
/
4.1. General
/
/
/
/
13C-NMR (in CDCl3) d 8.43, 128.32, 131.68, 133.14,
133.75; 29Si-NMR (in CDCl3) d 8.92. Anal. Found: C,
29.96; H, 2.98. Calc. for C7H8Br2Si: C, 30.02; H, 2.88%.
All reactions were carried out under an inert atmo-
sphere. NMR spectra were recorded on JEOL Model
JNM-EX 270 and JEOL Model JNM-LA 400 spectro-
meters. Mass spectra were measured with a Hitachi
M80B spectrometer.
Data for PhSiBr3: b.p. 58Á
178.3 8C/80 mmHg [9]); MS m/z 342 [Mꢁ], 265
[Mꢁ ÁPh], 263 [Mꢁ ÁBr], 184 [Mꢁ ÁBr2], 105 [Mꢁ Á
Br3]; 1H-NMR (CDCl3) d 7.26Á
7.56 (m, 3H), 7.80Á
/
69 8C/1 mmHg (Lit.
/
/
/
/
4.2. Materials
/
/
7.84 (m, 2H); 13C-NMR (CDCl3) d 128.44, 132.68,
132.96 (one carbon signal is overlapping). Anal. Found:
C, 21.20; H, 1.64. Calc. for C6H5Br3Si: C, 20.90; H,
1.46%.
Alkyl halides and allyl halides were distilled from
P2O5 and stored over molecular sieves in dark until use.
The starting hydrosilanes [7,11] and germanes [6a,10]
were prepared by the reactions of the respective
chlorides with lithium aluminum hydride.
Data for MePhSiI2: b.p. 145Á
m/z 374 [Mꢁ], 359 [Mꢁ ÁMe]; 1H-NMR (CDCl3) d
1.80 (s, 3H), 7.43Á7.76 (m, 3H), 7.72Á
7.75 (m, 2H); 13C-
/
150 8C/15 mmHg; MS
/
/
/
4.3. Halogenation of hydrosilanes and germanes
NMR (CDCl3) d 11.56, 128.16, 131.59, 133.23, 133.92.
Anal. Found: C, 22.49; H, 2.18. Calc. for C7H8SiI2: C,
22.48; H, 2.16%.
An illustrative procedure is as follows. A mixture of
PhMe2SiH (4.25 g, 31.3 mmol), n-PrBr (5.21 g, 42.4
mmol), and PdCl2 (75 mg, 0.42 mmol) was stirred at
80 8C for 12 h. After evaporation of excess n-PrBr, the
residue was fractionally distilled under reduced pressure
Data for HexSiI3: b.p. 85Á
494 [Mꢁ], 417 [Mꢁ ÁPh], 367 [Mꢁ Á
I3]; H-NMR (CDCl3) d 0.90 (t, 3H, Jꢀ
8.0 Hz,
/
95 8C/1 mmHg; MS m/z
I], 240 [Mꢁ Á
I2],
7.2
/
/
/
1
113 [Mꢁ Á
/
/
Hz, CH3), 1.31Á
/
1.49 (m, 8H), 2.15 (2H, t, Jꢀ
/
to give 6.34 g (b.p. 95Á
/
96 8C/17 mmHg, 29.5 mmol,
CH2Si); 13C-NMR (CDCl3) d 14.22, 22.46, 25.41, 30.12,
31.22, 32.40. Anal. Found: C, 14.75; H, 2.68. Calc. for
C6H13I3Si: C, 14.59; H, 2.65%.
94% yield) of PhMe2SiBr.
All spectral data obtained for iodosilanes Et2SiI2 and
Et2MeSiI [7] are identical with those reported in the
literature.
Data for PhSiI3: b.p. 140Á
486 [Mꢁ], 409 [Mꢁ ÁPh], 359 [Mꢁ Á
I3]; H-NMR (CDCl3) d 7.36Á
7.83 (m, 2H); 13C-NMR (CDCl3) d 128.03, 128.32,
132.38, 132.76.
Data for Et3GeBr: b.p. 130Á
190 8C [14]); MS m/z 240 [Mꢁ], 211 [Mꢁ Á
/
143 8C/2 mmHg; MS m/z
I], 232 [Mꢁ Á
I2],
7.52 (m, 3H),
/
/
/
Data for Et3SiBr: b.p. 58Á
163.2Á
163.3 8C/737 mmHg [9]); MS m/z 194 [Mꢁ], 165
[Mꢁ ÁEt], 137 [Mꢁ Á C H4], 115 [Mꢁ ÁBr]; 1H-NMR
EtÁ
7.7 Hz), 1.01 (q, 6H, Jꢀ
/
59 8C/18 mmHg (Lit. b.p.
1
105 [Mꢁ Á
7.79Á
/
/
/
/
/
/
/
/
2
(in CDCl3) d 0.89 (t, 9H, Jꢀ
/
/
7.7 Hz); 13C-NMR (in CDCl3) d 6.98, 7.77; 29Si-NMR
(in CDCl3) d 37.39. Anal. Found: C, 37.08; H, 7.48.
Calc. for C6H15BrSi: C, 36.92; H, 7.75%.
/
140 8C/80 mmHg (Lit.
Et], 182
3Et]; H-NMR (CDCl3) d 1.13Á
/
1
[Mꢁ Á
/
2Et], 153 [Mꢁ Á
/
/

94
A. Iwata et al. / Journal of Organometallic Chemistry 667 (2003) 90Á95
/
1.21 (m); 13C-NMR (CDCl3) d 8.52, 10.82. Anal.
Found: C, 30.02; H, 6.35. Calc. for C6H15BrGe: C,
30.07; H, 6.32%.
(m, 20H); 13C-NMR (CDCl3) d 14.00, 22.46, 26.17,
28.95, 30.75, 31.22. Anal. Found: C, 29.02; H, 5.23.
Calc. for C12H26I2Ge: C, 29.01; H, 5.28%.
Data for n-Hex3GeBr: b.p. 175Á
MS m/z 408 [Mꢁ], 329 [Mꢁ ÁBr], 323 [Mꢁ Á
[Mꢁ Á2Hex], 153 [Mꢁ Á3Hex]; 1H-NMR (CDCl3) d
0.88 (t, 9H, Jꢀ6.6 Hz), 1.18Á
1.53 (m, 30H); 13C-NMR
/
185 8C/1 mmHg;
Data for Ph2GeI2: b.p. 140Á
z 482 [Mꢁ], 405 [Mꢁ ÁPh], 355 [Mꢁ Á
1H-NMR (CDCl3) d 7.43Á
7.49 (m, 6H), 7.66 (dd, 4H,
Jꢀ
1.7, 6.3 Hz); 13C-NMR (CDCl3) d 128.61, 131.30,
/
150 8C/1 mmHg; MS m/
/
/
I], 228 [Mꢁ Á
/
2I];
/
/Hex], 238
/
/
/
/
/
/
(CDCl3) d 14.07, 19.45, 22.54, 24.53, 31.36, 32.35. Anal.
Found: C, 52.76; H, 9.92. Calc. for C18H39BrGe: C,
52.99; H, 9.63%.
132.61, 134.95. Anal. Found: C, 29.96; H, 2.07. Calc. for
C12H10I2Ge: C, 29.99; H, 2.10%.
Data for HexGeI3: b.p. 120Á
/
130 8C/1 mmHg; MS m/
I], 286 [Mꢁ Á
2I];
6.9 Hz), 1.30Á1.94
z 540 [Mꢁ], 455 [Mꢁ ÁHex], 413 [Mꢁ Á
/
/
/
Data for Ph3GeBr: b.p. 175Á
z 307 [Mꢁ ÁPh], 305 [Mꢁ ÁBr], 153 [Mꢁ Á
NMR (CDCl3) d 7.42Á7.45 (m, 9H), 7.60Á7.64 (m, 6H);
/
185 8C/1 mmHg; MS m/
3Ph]; 1H-
1H-NMR (CDCl3) d 0.90 (t, 3H, Jꢀ
/
/
/
/
/
(m, 10H); 13C-NMR (CDCl3) d 13.98, 22.41, 26.79,
28.74, 31.18, 38.92. Anal. Found: C, 13.66; H, 2.61.
Calc. for C6H13I3Ge: C, 13.38; H, 2.43%.
/
/
13C-NMR (CDCl3) d 128.61, 130.42, 134.21, 134.66.
Anal. Found: C, 56.03; H, 3.82. Calc. for C18H15BrGe:
C, 56.33; H, 3.94%.
Data for HeX2GeBr2: b.p. 155Á
m/z 402 [Mꢁ], 323 [Mꢁ ÁBr], 317 [Mꢁ Á
6.8 Hz), 1.30Á
/
165 8C/1 mmHg; MS
Hex]; 1H-NMR
1.71 (m, 20H);
/
/
(CDCl3) d 0.89 (t, 6H, Jꢀ
/
/
Acknowledgements
13C-NMR (CDCl3) d 14.00, 22.45, 24.23, 28.09, 31.23,
31.27. Anal. Found: C, 35.64; H, 6.80. Calc. for
C12H26Br2Ge: C, 35.79; H, 6.51%.
We thank Sankyo Kasei Co. Ltd and Sumitomo
Electric Industry for financial support, and Shin-Etsu
Chemical Co. Ltd for gifts of chlorosilanes.
Data for Ph2GeBr2: b.p. 160Á
m/z 386 [Mꢁ], 309 [Mꢁ ÁPh], 307 [Mꢁ Á
(CDCl3) d 7.48Á7.51 (m, 6H), 7.70Á
7.74 (m, 4H); 13C-
/
170 8C/1 mmHg; MS
1
/
/
Br]; H-NMR
/
/
NMR (CDCl3) d 128.91, 131.64, 132.67, 135.29. Anal.
Found: C, 37.46; H, 2.66. Calc. for C12H10Br2Ge: C,
37.28; H, 2.61%.
References
Data for HexGeBr3: b.p. 95Á
m/z 396 [Mꢁ], 317 [Mꢁ ÁBr], 238 [Mꢁ Á
6.6 Hz), 1.31Á
/
105 8C/1 mmHg; MS
2Br]; 1H-NMR
1.69 (m, 10H);
[1] (a) G.L. Larson, in: S. Patai, Z. Rappoport (Eds.), The Chemistry
of Organic Silicon Compounds (Part 1, Chapter 11), Wiley, New
York, 1989;
/
/
(CDCl3) d 0.89 (t, 3H, Jꢀ
/
/
13C-NMR (CDCl3) d 13.95, 22.34, 24.26, 30.03, 31.09,
37.54. Anal. Found: C, 18.23; H, 3.59. Calc. for
C6H13Br3Ge: C, 18.13; H, 3.30%.
(b) M.A. Brook, Silicon in Organic and Organometallic, and
Polymer Chemistry, Wiley, New York, 2000;
(c) D.A. Armitage, in: G. Wilkinson (Ed.), Comprehensive
Organometallic Chemistry I, vol. 2 (Chapter 1), Elsevier, London,
1982;
Data for Et3GeI: b.p. 130Á
212 8C [14]); MS m/z 288 [Mꢁ], 259 [Mꢁ Á
[Mꢁ Á2Et], 201 [Mꢁ Á3Et], 161 [Mꢁ ÁI]; 1H-NMR
/
140 8C/20 mmHg (Lit.
/Et], 230
(d) D.A. Armitage, in: E.W. Abel, F.G.A. Stone, G. Wilkinson
/
/
/
(Eds.), Comprehensive Organometallic Chemistry II, vol.
(Chapter 1), Elsevier, London, 1995.
2
(CDCl3) d 1.10 (t, 9H, Jꢀ
/
7.5 Hz), 1.29 (q, 6H, Jꢀ
/
7.5 Hz); 13C-NMR (CDCl3) d 9.62, 11.13. Anal. Found:
C, 25.12; H, 5.19. Calc. for C6H15IGe: C, 25.14; H,
5.27%.
[2] (a) H.S. Booth, J.F. Suttle, J. Am. Chem. Soc. 68 (1946) 2658;
(b) A.E. Newkirk, J. Am. Chem. Soc. 68 (1946) 2736;
(c) E. Hengge, F. Schrank, J. Organomet. Chem. 299 (1986) 1;
(d) E. Michel, W. Jung, A. Andrus, P.L. Ornstein, Tetrahedron
Lett. 48 (1977) 4175;
Data for n-Hex3GeI: b.p. 165Á
m/z 371 [Mꢁ ÁHex], 329 [Mꢁ ÁI], 286 [Mꢁ Á
3Hex]; H-NMR (CDCl3) d 0.88 (t, 9H, Jꢀ
Hz), 1.27Á
1.54 (m, 30H); 13C-NMR (CDCl3) d 14.08,
19.60, 22.54, 25.58, 31.34, 32.18. Anal. Found: C, 47.24;
H, 8.56. Calc. for C18H39IGe: C, 47.51; H, 8.64%.
/
175 8C/1 mmHg; MS
2Hex], 201
6.9
/
/
/
(e) H.R. Kricheldorf, Angew. Chem. Int. Ed. Engl. 9 (1979) 18;
1
[Mꢁ Á
/
/
(f) U. Kruerke, Chem. Ber. 95 (1962) 174.
¨
/
[3] For related works with synthetic equivalents of bromo- and
iodosilanes, see (a) J. Ohshita, A. Iwata, F. Kanetani, A. Kunai,
Y. Yamamoto, C. Matui, J. Org. Chem. 64 (1999) 8024;
(b) Y. Yamamoto, H. Shimizu, Y. Hamada, J. Organomet.
Chem., 16 (1996) 2204.
Data for Ph3GeI: b.p. 160Á
355 [Mꢁ ÁPh], 305 [Mꢁ ÁI], 201 [Mꢁ Á
(CDCl3) d 7.41Á
/
170 8C/1 mmHg; MS m/z
1
3Ph]; H-NMR
/
/
/
[4] R.D. Miller, D.R. McKean, Tetrahedron Lett. 25 (1975) 2305.
[5] For a related work with synthetic equivalents of iodosilanes,
Y. Yamamoto, C. Matui, Organometallics 16 (1997) 2204.
[6] (a) P. Rivie´re, M. Rivie´re-Baudet, J. Satge, in: G. Wilkinson (Ed.),
Comprehensive Organometallic Chemistry I, vol. 2 (Chapter 5),
Elsevier, London, 1982;
/
7.46 (m, 9H), 7.63 (dd, 6H, Jꢀ
/1.9, 6.8
Hz); 13C-NMR (CDCl3) d 128.63, 130.48, 134.05,
134.73. Anal. Found: C, 50.37; H, 3.36. Calc. for
C18H15IGe: C, 50.18; H, 3.51%.
Data for n-HeX2GeI2: b.p. 120Á
MS m/z 413 [Mꢁ ÁHex], 371 [Mꢁ ÁI], 328 [Mꢁ Á
1H-NMR (CDCl3) d 0.89 (t, 6H, Jꢀ
6.8 Hz), 1.30Á
/
130 8C/1 mmHg;
2Hex];
1.93
(b) P. Rivie´re, M. Rivie´re-Baudet, J. Satge, in: E.W. Abel, F.G.A.
Stone, G. Wilkinson (Eds.), Comprehensive Organometallic
Chemistry II, vol. 2 (Chapter 5), Elsevier, London, 1995.
/
/
/
/
/

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