A new catalytic route to synthesis of silylgermylethynes

Article abstract of DOI:10.1016/j.jorganchem.2007.10.039

Silylgermylethynes known to be potential organometallic reagents and precursors of optoelectronic materials can be efficiently synthesized via a recently reported catalytic method called silylative coupling of alkynes with vinylsilicon compounds. The reaction of triethylethynylgermane with vinyltrisubstituted silanes catalyzed by [RuHCl(CO)(PR₃)_n] (where R = ⁱPr, Cy, Ph; n = 2-3) under optimal conditions selectively yields respective silylgermylethynes. Silylation of ethynylgermane with divinylsilicon derivatives such as siloxanes, silazanes, bis(silyl)benzene and bis(silyl)ethane gives monoethynylgermyl substituted vinyldisilicon products with high yields and selectivity, however, accompanied by traces of dialkynylgermyl derivatives. All catalytic results as well as those of stoichiometric study on the insertion of ethynylgermane into Ru-Si bond have permitted proposing mechanistic schemes of the reaction examined.

Full text of DOI:10.1016/j.jorganchem.2007.10.039

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Journal of Organometallic Chemistry 693 (2008) 235–240
www.elsevier.com/locate/jorganchem
A new catalytic route to synthesis of silylgermylethynes
Bogdan Marciniec *, Hanna Ławicka, Beata Dudziec
Adam Mickiewicz University, Faculty of Chemistry, Department of Organometallic Chemistry, Grunwaldzka 6, 60-780 Poznan, Poland
Received 16 August 2007; received in revised form 22 October 2007; accepted 24 October 2007
Available online 30 October 2007
Abstract
Silylgermylethynes known to be potential organometallic reagents and precursors of optoelectronic materials can be efficiently syn-
thesized via a recently reported catalytic method called silylative coupling of alkynes with vinylsilicon compounds. The reaction of tri-
ethylethynylgermane with vinyltrisubstituted silanes catalyzed by [RuHCl(CO)(PR3)n] (where R = iPr, Cy, Ph; n = 2–3) under optimal
conditions selectively yields respective silylgermylethynes. Silylation of ethynylgermane with divinylsilicon derivatives such as siloxanes,
silazanes, bis(silyl)benzene and bis(silyl)ethane gives monoethynylgermyl substituted vinyldisilicon products with high yields and selec-
tivity, however, accompanied by traces of dialkynylgermyl derivatives. All catalytic results as well as those of stoichiometric study on the
insertion of ethynylgermane into Ru–Si bond have permitted proposing mechanistic schemes of the reaction examined.
Ó 2007 Elsevier B.V. All rights reserved.
Keywords: Ethynylgermane; C–H activation; Homogeneous catalysis; Ruthenium; Silanes
1. Introduction
metathesis (for comparison of these reactions see [5] and
[11]) and proceeds according to the following general Eq.
(1):
Functionalized alkynylsilanes and alkynylgermanes are
used separately as alkynylation agents in synthesis of
organic, organometallic and natural products [1]. More-
over, both silicon and germanium compounds possessing
p-conjugated systems have been considered (also as com-
bined silicon germanium derivatives) as potential precur-
sors of optoelectronic materials, particularly candidates
for electronic devices [2]. Alkynyl derivatives of silicon
and germanium can be prepared by various methodologies
involving classical stoichiometric routes from organometal-
lic reagents [3] as well as more recently (particularly alky-
nylsilanes) by metal-catalyzed silylation of terminal
alkynes [4].
R'nE
H
R'nE
R'nE
H
H
R
H
R
H
H
(M E)
H
M
+
+
C
C
C
C
C
C
C C
H
H
R
H
H
where E = Si, B, Ge
R = Ph, OR", NR2, OCOR"
M = Ru, Rh, Ir
R' = alkyl, aryl, alkoxyl
ð1Þ
The reaction occurs by activation of sp2 carbon–hydro-
gen bond and sp2 carbon–heteroatom (E) bond. Very
recently we have reported on the activation of sp-hybrid-
ized carbon–hydrogen bonds by such vinyl metalloids (par-
ticularly by vinylsilicon [8] and vinylgermanium [9]
derivatives). The reaction (see Eq. (2)), called the cross-
coupling of alkynes with vinylsilicon and vinylgermanium
compounds, proceeds in the presence of complexes con-
taining [Ru]–H and/or [Ru]–Si bonds. Only in some cases
the target silylethynes and germylethynes have been accom-
panied by products of homo-coupling of vinylmetaloid
compounds used in excess.
In the last two decades we have developed a new type of
transition metal-catalyzed reaction of vinylsubstituted
organoelement (E) (where E = Si, Ge, B) compounds with
olefins called silylative (for review see [5]), germylative [6]
and borylative [7] coupling that is complementary to olefin
*
Corresponding author. Tel.: +48 0618291366; fax: +48 0618291508.
E-mail address: bogdan.marciniec@amu.edu.pl (B. Marciniec).
0022-328X/$ - see front matter Ó 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2007.10.039

236
B. Marciniec et al. / Journal of Organometallic Chemistry 693 (2008) 235–240
ER3
[Ru]
(4)). However, in all cases the main products were accom-
panied by traces of dialkynylgermyl derivatives (Table 2).
There should be emphasized that, in view of the known
synthetic procedures, monoethynylgermyl substituted
vinyldisilicon products, especially with both acetylene and
vinyl functionalities are difficult to be synthesized by other
methods. This fact may be crucial to admit the great impor-
tance of the silylation of ethynylgermane with divinylsil-
icon derivatives reported here.
The results of catalytic experiments on silylation of
ethynylgermane and previously reported stoichiometric
study of insertion of acetylenes into Ru–Si bond [8–10]
allow us to propose the following mechanistic scheme of
the reaction studied (Scheme 1):
R3E
R'
+
+ H
R'
R3E
toluene
-
R3E
where E = Ge, Si
(by-product)
product of
homo-coupling of vinylmetaloid
ð2Þ
The aim of the study reported here is to show the possi-
bility of application of the new catalytic route involving
coupling of ethynylgermane with vinylsilicon compounds
for selective synthesis of silylgermylethynes, otherwise
difficult to achieve using alternative synthetic routes.
2. Results and discussion
The reaction scheme involves an insertion of ethynylger-
mane into the [Ru]–Si bond (via route proposed earlier,
regarding the way of cis–trans isomerisation; see [11])
followed by elimination of silylethynylgermane product
(for mechanistic consideration see [10]). The consecutive
Similarly to the previous reports [8a,9] [RuHCl
(CO)(PCy3)2] and [RuHCl(CO)(PPh3)3] appeared to be
the most effective catalysts in the following reaction (see
Eq. (3)):
[Ru]
SiR3
R3Si
+
R3Si
GeEt3
+
H
GeEt3
R3Si
toluene
-
ð3Þ
(a)
(b)
product of
homo-coupling of vinylsilane
[Ru]
+
GeEt3
+
GeEt3
Et3Ge
R
R
GeEt3
R
toluene
-
ð4Þ
(a)
(b)
Table 1
Catalytic transformation of triethylethynylgermane via cross-coupling
with vinylsilanes
The reaction was successfully performed under argon
atmosphere (open glass ampoules) in 100 °C, its products
were detected by GC and GC–MS methods and identified
by 1H and 13C NMR spectroscopy. Triethylethynylger-
mane was used as a substrate in this reaction (Table 1).
Silylation of ethynylgermane derivatives required more cat-
alyst (2%) rather than the used in silylation (1%), however
reducing the amount of catalyst affects only the time of the
reaction (48 not 24 h), not the selectivity [9].
As we have found [8a] the equimolar reaction of vinylsil-
anes with alkynes gives some enynes as products of alkyne
dimerization. For exclusion of enynes, vinylsilanes must be
used in excess. On the other hand, a twofold excess of
vinylsilane yields silylgermylethynes but accompanied by
a product of vinylsilane homo-coupling. The reaction con-
ditions needed to be optimized for the exclusive formation
of the product desired and the 1.5-fold excess of vinylsil-
icon compounds was the best amount to be employed.
Silylation of ethynylgermane by divinylsubstituted
silicon compounds at a twofold excess of vinylsilicon
substrate gives monoethynylgermyl substituted vinyldisil-
icon products with high yields and selectivity (see Eq.
Conversion of Selectivity (%) a/b (refers to the
SiR3
Et3GeC„CH compounds a and b) a – major
(%)
product
87
100
SiMe2Ph
52a
41b
90c
75d
76
97/3
100
92/2
93/5
99/1
Si(OEt)3
32
61c
100
98/2
SiMe(OSiMe3)2
57
99c
100
96/4
SiMe2(OSiMe3)
Reaction conditions: Ar, open glass ampoules, toluene (0.5 M), t = 24 h,
T = 100 °C.
[Ru] = [RuHCl(CO)(PCy3)2], [Ge] = [Et3GeC„CH], [Si] = [R3SiCH
CH2].
[Ru]:[Ge]:[Si] = 2 ꢀ 10ꢁ2:1:1.5.
a
[Ru]:[Ge]:[Si] = 10ꢁ2:1:2.
b
[RuHCl(CO)(PPh3)3]:[Ge]:[Si] = 2 ꢀ 10ꢁ2:1:1.5.
c
[Ru]:[Ge]:[Si] = 2 ꢀ 10ꢁ2:1:2.
d
[Ru(SiMe3)Cl(CO)(PCy3)2]:[Ge]:[Si] = 2 ꢀ 10ꢁ2:1:1.5.

B. Marciniec et al. / Journal of Organometallic Chemistry 693 (2008) 235–240
237
Table 2
the reaction of equimolar amounts of [Ru(SiMe3)Cl
(CO)(PPh3)2] with triethylethynylgermane which occurs
as follows (Scheme 2): (identified by 1H NMR spectroscopy
and GC–MS).
Catalytic transformation of triethylethynylgermane via cross-coupling
with divinylsilicon derivatives catalyzed by [RuHCl(CO)(PCy3)2]
No.
Conversion
of
Selectivity (%) a/b
(refers to the
R
The spectra allowed a detection of formation of the
[Ru]–H complex (confirmed by the appearance of a doublet
of triplets at ꢁ6.63 ppm (JH–P = 105.2 Hz, JH–P = 24.3 Hz))
– a product of acetylene insertion into [Ru]–Si complex,
followed by the elimination of the substituted ethyne com-
pound (see Fig. 1a). There is a visible decrease in the
amount of [Ru]–H moiety as temperature rises. The created
in situ [Ru]–H complex and triethylethynylgermane (pres-
ent in the system in slight excess – see Section 4) reacted
towards ruthenium–vinylene complex and this progress of
the reaction was also controlled by NMR analysis. The
amount of the vinylene complex increased with increasing
temperature (see Fig. 1b). In the absence of vinylgermane
[8a,10], the [Ru]–H complex is active in the hydrogenation
of acetylenes (see the ratios of compounds after the com-
pletion of the equimolar reaction (Scheme 2).
Et3GeC„CH compounds a and b) a
(%)
– major product
1
Me
Si
Me
Si
99
90/10
Me
Me
Me
Me
Si
2
3
4
5
6
68
74
70
0a
95/5
95/5
94/6
Si
O
Me
Me
Me H Me
Si
N
Si
Me
Me
OEt OEt
Si Si
O
OEt OEt
Me
Si
Me
Me Me
12
Mixture of
Si Si
3. Conclusion
unidentified products
Me Me
Me
Si
In conclusion, we have shown that the new general
reaction of silylative coupling of acetylenes catalyzed by
[RuHCl(CO)(PCy3)2] or [RuHCl(CO)(PPh3)3], reported
here, can be a valuable tool for selective synthesis of
silylethynylgermanes and vinylsilylgermylalkynyl deriva-
tives of both, acetylene and vinyl functionalities. These
compounds may play a very important role as potent
organometallic reagents and precursors of e.g. optoelec-
tronic materials.
Me
Si
7
86
97/3
Me
Me
Reaction conditions: open system, toluene (0.5 M), t = 24 h, 110 °C.
[RuHCl(CO)(PCy3)2]:[Et3GeC„CH]:[(CH2@CH)2R] = 2 ꢀ 10ꢁ2:1:2.
a
Closed system.
insertion of vinylsilicon compounds into the [Ru]–H bond
followed by b-Si-elimination of ethylene is well-docu-
mented [7].
4. Experimental
Although this general mechanism had been proved by
the stoichiometric study reported earlier [8a] we performed
4.1. General methods
1H NMR (300 MHz), 13C NMR (75 MHz) and DEPT
spectra were recorded on a Varian XL 300 MHz spectrom-
eter in CDCl3 (or C6D5CD3) solution. Chemical shifts are
reported in d (ppm) with reference to the residue portion
R3E
R'
[Ru]
H
ER3
1
H
solvent (CHCl3) peak assigned to H and 13C NMR. Gas
ER3
chromatographic (GC) analyses were performed on a Var-
ian 3300 with a DB-5 fused silica capillary column
(30 m ꢀ 0.15 mm) and TCD. Mass spectra of the mono-
mers and products were obtained by GC–MS analysis
(Varian Saturn 2100 T, equipped with a BD-5 capillary col-
umn (30 m) and an ion trap detector). Thin-layer chroma-
tography (TLC) was made on plates coated with 250 lm
thick silica gel (Aldrich and Merck), and column chroma-
tography was conducted with Silica Gel 60 (70–230 mesh,
Fluka).
[Ru]
H
H
R'
[Ru]
H
ER3
R3E
H
H
[Ru]
R'
R'
[Ru]
ER3
4.2. Materials
E = Ge, Si
The chemicals were obtained from the following
sources: toluene, dodecane, pentane and hexane, were
Scheme 1. Mechanism of coupling of triethylethynylgermane with vinyl-
substituted silicon compounds.

238
B. Marciniec et al. / Journal of Organometallic Chemistry 693 (2008) 235–240
GeEt3
-20oC - +60oC, C6D5CD3
PPh3
PPh3
H
Cl
Cl
GeEt3
[Ru]-H
Ru
Ru SiMe3
PPh3
-
GeEt3
Me3Si
GeEt3
observed at
low temperature
CO
CO
PPh3
H
Et3Ge
SiMe3
+
:
GeEt3
3.6
+
:
+
GeEt3
SiMe3
traces
4.7
1
:
Scheme 2. The reaction of equimolar amounts of [Ru(SiMe3)Cl(CO)(PPh3)2] with triethylethynylgermane.
Fig. 1. Temperature dependence of the 1H NMR spectra of the reaction of [Ru(SiMe3)Cl(CO)(PPh3)2] with triethylethynylgermane.
purchased from Fluka, CDCl3, C6D5CD3 from Dr. Glaser
A.G. Basel. The substituted acetylenes were bought from
Aldrich. The HC„CGeEt3 were prepared according to
the literature procedure [9]. The ruthenium complexes
[RuHCl(CO)(PCy3)2], [RuHCl(CO)(PPh3)3], [Ru(SiMe3)-
Cl(CO)(PPh3)2] were prepared according to the literature
procedure [12]. Toluene and pentane were dried by distilla-
tion from sodium hydride, similarly hexane was distilled
from calcium hydride under argon. All liquid substrates
were also dried and degassed by bulb-to-bulb distillation.
All the reactions were carried out under dry argon
atmosphere.
(ꢁ50 °C) was added. The supernatant was removed and
the yellow precipitate was washed three times with pentane
(at ꢁ50 °C) and dried in vacuo. Yield 85%.
Analytical data: 1H NMR (C6D6; d (ppm)): 0.31 (s, 9H,
SiCH3), 1.18–2.60 (m, 33H, P(C6H11)3); 13C NMR (C6D6; d
(ppm)): 1.62 (SiCH3), 26.75–35.28 (P(C6H11)3), 202.10
(CO); 31P NMR (C6D6; d (ppm)): 46.63 (P(C6H11)3).
4.4. The reaction of equimolar amounts of
[Ru(SiMe3)Cl(CO)(PPh3)2] with triethylethynylgermane
In
a test, the ruthenium catalyst [Ru(SiMe3)Cl
4.3. Procedure for synthesis of
[Ru(SiMe3)Cl(CO)(PCy3)2]
(CO)(PPh3)2] was dissolved in toluene-d8 and placed in
an NMR ampoule under argon. The ampoule was cooled
in liquid nitrogen then triethylethynylgermane was added
(at the molar ratio: [Ru]:[triethylethynylgermane] = 1:1.2).
After that, the ampoule was inserted into a Brucker Ultra
Shield spectrometer (600 MHz) and slowly heated. The
spectra were recorded at different temperatures between
ꢁ20 and +60 °C, changed at a step of 10 °C.
H2C@CHSiMe3 (0.243 mL, 1.7 mmol) was added via a
syringe to the refluxing solution of [RuHCl(CO)(PCy3)2]
(244 mg, 0.34 mmol) in benzene (10 mL) and the reaction
mixture was refluxed for 72 h. The solvent was evaporated
under reduced pressure and 15 mL of cold pentane

B. Marciniec et al. / Journal of Organometallic Chemistry 693 (2008) 235–240
239
4.5. Representative procedure for synthesis of [Et3Ge–C„
C–SiR3]
4.6.3. 1-Bis(trimethylsiloxy)methylsilyl-2-(triethylgermyl)-
ethyne
1
Analytical data: H NMR (CDCl3; d (ppm)): 0.14 (s,
In a typical test, the ruthenium catalyst [RuH(Cl)
(CO)(PCy3)2] (2 mol%) was dissolved in toluene and placed
in a glass ampoule under argon. Then the reagents and
decane as internal standard (5% by volume all compo-
nents), triethylethynylgermane and vinylsilane (usually
used at the molar ratio: [Ru]:[Et3GeC„CH]:[R3SiCH@
CH2] = 2 ꢀ 10ꢁ2:1:1.5 or 2 ꢀ 10ꢁ2:1:2) were added. After
that, the ampoule was heated to 100 °C and maintained
at that temperature for 24 h. The final products were sepa-
rated from the residues of the catalyst and reactants by
using a column with silica. The progress of the reaction
was controlled by GC and GC–MS. All products of
catalytic transformation of triethylethynylgermane and
vinylsilane were oily liquids.
18H, OSiCH3), 0.16 (s, 3H, SiCH3), 0.87 (q, 6H,
GeCH2CH3, JH–H= 8.1 Hz), 1.09 (t, 9H, GeCH2CH3,
JH–H= 8.1 Hz).
13C NMR (CDCl3; d (ppm)): 1.79 (OSiCH3), 2.00
(SiCH3), 5.68 (GeCH2CH3), 9.01 (GeCH2CH3), 108.78
(Ge–C„C), 112.96 (Si–C„C).
MS (EI) [m/z (%)] = 377 (M+ÅꢁCH2CH3, 20), 363 (33),
349 (100), 321 (25), 231 (6), 215 (17), 201 (8), 147 (25), 133
(31), 119 (29), 73 (33), 59 (4). Elemental Anal. Calc. for
C15H36GeO2Si3: C. 44.45; H, 8.95; O, 7.87. Found: C,
44.41; H, 8.96; O, 7.84%. Isolated yield 55%.
4.6.4. 1-(Trimethylsiloxy)dimethylsilyl-2-(triethylgermyl)-
ethyne
Analytical data: MS (EI) [m/z (%)] = 333 (M+Å, 1), 289
(M+ÅꢁSiCH3, 17), 275 (M+ÅꢁCH2CH3, 100), 247 (61),
171 (3), 157 (15), 143 (14), 103 (4), 89 (5), 73 (17), 59 (3).
4.6. Representative procedure for synthesis of [H2C@CH–R–
C„C–GeEt3 and Et3Ge–C„C–R–C„C–GeEt3]
In a typical test, the ruthenium catalyst [RuH(Cl)
(CO)(PCy3)2] (2 mol%) was dissolved in toluene and placed
in a glass ampoule under argon. Then the reagents and dec-
ane as internal standard (5% by volume all components),
triethylethynylgermane and divinylsilane (at the molar
ratio: [Ru]:[Et3GeC„CH]:[(CH2@CH)2R] = 2 ꢀ 10ꢁ2:1:2)
were added. After that, the ampoule was heated to
110 °C and maintained at that temperature for 24 h. The
final products were separated from the residues of the
catalyst and reactants by using a column with silica. The
progress of the reaction was controlled by GC and
GC–MS. All products of catalytic transformation of trieth-
ylethynylgermane and divinylsilicon compound were oily
liquids.
4.6.5. 1-[(Triethylgermylethynyl)dimethylsilyl]-4-(dimethy-
lvinylsilyl)benzene
1
Analytical data: H NMR (CDCl3; d (ppm)): 0.35 (s,
6H, SiCH3), 0.39 (s, 6H, SiCH3), 0.89 (q, 6H, GeCH2CH3,
JH–H= 8.1 Hz), 1.11 (t, 9H, GeCH2CH3, JH–H= 8.1 Hz),
5.76 (dd, 1H, Si–HC@CH2), 6.06 (dd, 1H, Si–HC@CH2),
6.29 (dd, 1H, Si–HC@CH2), 7.56 (d, 2H, C6H4), 7.65 (d,
2H, C6H4).
13C NMR (CDCl3; d (ppm)): ꢁ2.88 (SiCH3), ꢁ0.40
(SiCH3), 5.85 (GeCH2CH3), 9.08 (GeCH2CH3), 111.42
(Ge–C„C), 113.93 (Si–C„C), 132.75 (Si–CH@CH2),
132.92 (CH), 133.01 (CH), 137.76 (Si–CH@CH2), 138.13
(ci-C6H4), 139.37 (ci-C6H4).
MS (EI) [m/z (%)] = 375(M+ÅꢁCH2CH3, 100), 347 (90),
319 (57), 291 (35), 271 (6), 257 (10), 215 (20), 187 (9), 161
(19), 145 (24), 131 (15), 105 (9), 73(24), 59 (32). Elemental
Anal. Calc. for C20H34GeSi2: C, 59.56; H, 8.50; O, 7.87.
Found: C, 59.50; H, 8.48%. Isolated yield 92%.
4.6.1. 1-Phenyldimethylsilyl-2-(triethylgermyl)ethyne
1
Analytical data: H NMR (CDCl3; d (ppm)): 0.41 (s,
6H, SiCH3), 0.86 (q, 6H, GeCH2CH3, JH–H = 8.1 Hz),
0.92 (t, 9H, GeCH2CH3, JH–H = 8.1 Hz), 7.36–7.69 (m,
5H, CH).
4.6.6. 1-[(Triethylgermylethynyl)]-1,1,3,3-tetramethyl-3-
vinyl-disiloxane
13C NMR (CDCl3; d (ppm)): ꢁ0.37 (SiCH3), 5.85
(GeCH2CH3), 9.08 (GeCH2CH3), 111.58 (Ge–C„C),
113.88 (Si–C„C), 127.65 (CH), 129.11 (CH), 133.62
(CH), 137.37 (ci-C6H5).
1
Analytical data: H NMR (CDCl3; d (ppm)): 0.19 (s,
6H, SiCH3), 0.22 (s, 6H, SiCH3), 0.87 (q, 6H, GeCH2CH3,
JH–H= 8.1 Hz), 1.07 (t, 9H, GeCH2CH3, JH–H= 8.1 Hz),
5.76 (dd, 1H, Si–HC@CH2), 5.94 (dd, 1H, Si–HC@CH2),
6.16 (dd, 1H, Si–HC@CH2).
MS (EI) [m/z (%)] = 319 (M+, 3), 291 (M+ÅꢁCH2CH3,
100), 263 (65), 235 (22), 171 (3), 159 (12), 145 (13), 105
(8), 89 (4), 75 (8), 53 (4). Elemental Anal. Calc. for
C16H26Ge: C, 60.22; H, 8.21. Found: C, 60.18; H, 8.22%.
Isolated yield 80%.
13C NMR (CDCl3; d (ppm)): 2.45 (SiCH3), 2.61
(SiCH3), 5.74 (GeCH2CH3), 9.02 (GeCH2CH3), 110.75
(Ge–C„C), 113.49 (Si–C„C), 131.61 (Si–CH@CH2),
139.17 (Si–CH@CH2).
MS
(EI)
[m/z
(%)] = 343
(M+Å,
1),
287
(M+Åꢁ2 ꢂ CH2CH3, 100), 259 (54), 231 (8), 197 (6), 183
(12), 169 (37), 143 (19), 117 (13), 103 (10), 73 (24), 59 (8).
Elemental Anal. Calc. for C14H30GeOSi2: C, 48.99; H,
8.81; O, 4.66. Found: C, 49.03; H, 8.84; O, 4.70%. Isolated
yield 60%.
4.6.2. 1-Triethoxysilyl-2-(triethylgermyl)ethyne
Analytical
data:
MS
(EI)
[m/z
(%)] = 319
(M+ÅꢁCH2CH3, 22), 291 (100), 275 (11), 263 (34), 247
(39), 219 (20), 203 (15), 189 (9), 175 (10), 161 (12), 133
(10), 101 (7), 73 (5).

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B. Marciniec et al. / Journal of Organometallic Chemistry 693 (2008) 235–240
(d) F. David-Quillot, D. Marsacq, A. Balland, J. Thibonnet, M.
Abarbri, A. Ducheˆne, Syntheses (2003) 448;
(e) D. Wrackmeyer, O.L. Tok, E. Klimkina, Y.N. Bubnov, J.
Organomet. Chem. 620 (2001) 51;
4.6.7. 1-[(Triethylgermylethynyl)dimethylsilyl]-2-(dimethy-
lvinylsilyl)ethane
1
Analytical data: H NMR (CDCl3; d (ppm)): 0.05 (s,
6H, SiCH3), 0.07 (s, 6H, SiCH3), 0.53 (m, 4H, CH2–CH2),
0.85 (q, 6H, GeCH2CH3, JH–H= 8.1 Hz), 1.07 (t, 9H,
GeCH2CH3, JH–H = 8.1 Hz), 5.67 (dd, 1H, Si–HC@CH2),
5.92 (dd, 1H, Si–HC@CH2), 6.14 (dd, 1H, Si–HC@CH2).
13C NMR (CDCl3; d (ppm)): ꢁ3.96 (SiCH3), ꢁ2.11
(SiCH3), 5.69 (GeCH2CH3), 7.39 (–CH2–CH2–), 8.55
(–CH2–CH2–), 8.95 (GeCH2CH3), 111.83 (Ge–C„C),
113.39 (Si–C„C), 131.52 (Si–CH@CH2), 139.02
(Si–CH@CH2).
(f) J. Sauer, D.K. Hetzenegger, J. Krauthan, H. Sichert, J. Schuster,
Eur. J. Org. Chem. 1998 (1998) 2885;
(g) J.W. Faller, R.G. Kultyshev, Organometallics 21 (2002)
5911.
[2] L. Ding, W. Wong, H. Xiang, S. Poon, F.E. Karasz, Synth. Met. 156
(2006) 110.
[3] (a) R. Eastmond, D.R.M. Walton, Tetrahedron 28 (1972) 4591;
(b) P. Mazerolles, Bull. Soc. Chim. Fr. (1960) 856;
(c) A. Chrostowska, V. Metail, G. Pfister-Guillouzo, J.C. Guillemin,
J. Organomet. Chem. 564 (1998) 175;
(d) W. Leong, C. So, K. Chong, K. Kan, H. Chan, T.C.W. Mak,
Organometallics 25 (2006) 2851;
MS (EI) [m/z (%)] = 326 (M+ÅꢁCH2CH3, 17), 313 (10),
299 (67), 271 (50), 243 (15), 209 (15), 195 (100), 181 (20),
155 (22), 129 (18), 103 (12), 85 (31), 73 (16), 59 (86). Ele-
mental Anal. Calc. (%) for C16H34GeSi2: C, 54.09; H,
9.65. Found: C, 54.13; H, 9.62%. Isolated yield 82%.
(e) W. Kitching, K. Kwetkat, Alkynylarsenic, - antimony, - bismuth,
-boron, -silicon, -germanium and -metal Compounds, in: A.R.
Katritzky, O. Methcohn, C.W. Rees (Eds.), Comprehensive Organic
Functional Group Transformations, vol. 2, Elsevier Science, Oxford,
1995, p. 1083 (Chapter 2.23).
[4] D. Fletcher, Alkynylarsenic, -antimony, -bismuth, -boron, -silicon,
-germanium, and -metal Compounds, in: A.R. Katritzky, R.J.K.
Taylor (Eds.), Comprehensive Organic Functional Group Transfor-
mations II, vol. 1, Elsevier Science, Oxford, 2005, p. 1171 (Chapter
2.23).
[5] (a) B. Marciniec, C. Pietraszuk, I. Kownacki, M. Zaidlewicz, Vinyl-
and Arylsilicon, Germanium, and Boron Compounds, in: A.R.
Katritzky, R.J.K. Taylor (Eds.), Comprehensive Organic Functional
Group Transformations II, vol. 2, Elsevier Science, Oxford, 2005, p.
941 (Chapter 2.18), and references cited therein;
(b) B. Marciniec, Coord. Chem. Rev. 249 (2005) 2374;
(c) B. Marciniec, C. Pietraszuk, Curr. Org. Chem. 7 (2003) 691.
[6] B. Marciniec, H. Ławicka, M. Majchrzak, M. Kubicki, I. Kownacki,
Chem. Eur. J. 12 (2006) 244.
4.6.8. 1-[(Triethylgermylethynyl)]-1,1,3,3-tetraethoxy-3-
vinyl-disiloxane
Analytical data: MS (EI) [m/z (%)] = 465 (M+Å, 1), 351
(66), 291 (100), 259 (28), 247 (22), 215 (13), 199 (12), 159
(12), 129 (7), 101 (7), 73 (6).
4.6.9. 1-[(Triethylgermylethynyl)]-1,1,3,3-tetramethyl-3-
vinyl-disilazane
Analytical
data:
MS
(EI)
[m/z
(%)] = 465
(M+ÅꢁCH2CH3, 18), 286 (100), 258 (70), 216 (11), 196
(11), 182 (44), 168 (44), 154 (19), 142 (35), 116 (16), 100
(24), 73 (23), 59 (11).
[7] B. Marciniec, M. Jankowska, C. Pietraszuk, Chem. Commun. (2005)
663.
[8] (a) B. Marciniec, B. Dudziec, I. Kownacki, Angew. Chem., Int. Ed.
45 (2006) 8180;
Acknowledgement
(b) B. Marciniec, B. Dudziec, K. Szubert, Polish Patent Appl. P 380
422, 2006.
[9] B. Marciniec, H. Ławicka, B. Dudziec, Organometallics 26 (2007)
5188.
[10] B. Marciniec, Acc. Chem. Res. 40 (2007) 943.
[11] (a) Ch.-H. Jun, R.H. Crabtree, J. Organomet. Chem. 447 (1993)
177;
This work was supported by the Ministry of Science and
Higher Education (Poland) (Grant PBZ-KBN 118/T09/
17).
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