Hydrosilylation of 1,4-bis(trimethylsilyl)-1-buten-3-ynes using late transition metal hydrides as catalyst precursors

Article abstract of DOI:10.1016/S0022-328X(00)00189-3

Two geometrical isomers of 1,4-bis(trimethylsilyl)-1-buten-3-yne (cis- and trans-1) were subjected to catalytic hydrosilylation with HSiR₃ (HSiMe₂Ph or HSiMePh₂) in the presence of catalytic amounts of late transition meta

Full text of DOI:10.1016/S0022-328X(00)00189-3

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Journal of Organometallic Chemistry 609 (2000) 130–136
Hydrosilylation of 1,4-bis(trimethylsilyl)-1-buten-3-ynes using late
transition metal hydrides as catalyst precursors
Yooichiroh Maruyama, Keigo Yoshiuchi, Fumiyuki Ozawa *
Department of Applied Chemistry, Faculty of Engineering, Osaka City Uni6ersity, Sumiyoshi-ku, Osaka 558-8585, Japan
Received 14 February 2000; received in revised form 14 March 2000
Abstract
Two geometrical isomers of 1,4-bis(trimethylsilyl)-1-buten-3-yne (cis- and trans-1) were subjected to catalytic hydrosilylation
with HSiR3 (HSiMe2Ph or HSiMePh2) in the presence of catalytic amounts of late transition metal hydrides. Four kinds of regio-
and stereoisomers of hydrosilylation products were formed: (R3Si)(Me3Si)CꢀCꢀCHCH2SiMe3 (2), (1Z,3E)-CH(SiMe3)ꢀC(SiR3)-
CHꢀCHSiMe3 (3), (1Z,3E)-C(SiMe3)(SiR3)ꢀCHCHꢀCHSiMe3 (4), and (1E,3E)-C(SiMe3)(SiR3)ꢀCHCHꢀCHSiMe3 (5). The
product selectivity was strongly affected by the geometry of 1 as well as the catalyst precursor employed. Compounds 2–5 could
be prepared in over 93% selectivity, respectively. © 2000 Elsevier Science S.A. All rights reserved.
Keywords: Catalytic hydrosilylation; 1,4-Bis(trimethylsilyl)-1-buten-3-yne; Platinum catalyst; Rhodium catalyst; Ruthenium catalyst
bis(trimethylsilyl)-1-buten-3-yne (cis-1) into RuH-
1. Introduction
Cl(CO)(PPh3)3 took place selectively at the double
bond, giving an h3-propargyl/allenyl complex
A
Insertion of
a
CꢁC multiple bond into
a
(Scheme 1) [2]. In contrast, the trans isomer (trans-1)
underwent the insertion at the triple bond to give an
h3-butadienyl complex B [3,4]. Thus, a clear depen-
dence of the insertion site upon the geometry of 1 has
been documented.
metalꢁhydrogen bond is a crucial elementary process in
transition metal-catalyzed transformation of unsatu-
rated hydrocarbons [1]. In general, a double bond is
less reactive than a triple bond. However, Wakatsuki et
al. previously reported that the insertion of cis-1,4-
We have been interested in this unique phenomenon
found by Wakatsuki et al. and attempted in this study
its application to catalytic reactions. That is, the two
geometrical isomers of butenynes (cis-1 and trans-1)
were subjected to catalytic reactions including hydro-
genation, hydrosilylation and hydroboration, and effect
of the geometry upon product-selectivity was examined
in the presence of catalytic amounts of late transition
metal complexes [5]. Although no notable results were
obtained for hydrogenation and hydroboration, the
structures of hydrosilylation products were effectively
altered by the starting butenynes as well as catalyst
precursors. Thus, as summarized in Scheme 2, four
kinds of regio- and stereoisomers (2–4) could be ob-
tained in over 93% selectivities, respectively. Allenylsi-
lane 2 is a 1,4-adduct of hydrosilane across the
butenyne skeleton of 1. Silylbutadienes 3, 4 and 5 are
Scheme 1.
* Corresponding author. Fax: +81-6-66052978.
E-mail address: ozawa@a-chem.eng.osaka-cu.ac.jp (F. Ozawa).
0022-328X/00/$ - see front matter © 2000 Elsevier Science S.A. All rights reserved.
PII: S0022-328X(00)00189-3

Y. Maruyama et al. / Journal of Organometallic Chemistry 609 (2000) 130–136
131
Scheme 2.
Table 1
Hydrosilylation of cis- and trans-1 in the presence of platinum catalysts a
Entry
Butenyne
Catalyst
Hydrosilane
Reaction time (h)
Product ratio b
Total yield (%) c
2
3
4
5
1
2
3
4
5
6
cis-1
H2PtCl6·6H2O
H2PtCl6·6H2O
PtCl2(cod)
Pt(cod)2
PtCl2(PPh3)2
Pt(PPh3)4
HSiMe2Ph
HSiMePh2
HSiMePh2
HSiMePh2
HSiMePh2
HSiMePh2
3
123
93
69
143
23
96
94
92
94
3
4
6
8
6
76
75
0
0
0
0
0
0
0
0
0
0
21
22
100
94
89
96
98
3
100
7
trans-1
H2PtCl6·6H2O
H2PtCl6·6H2O
PtCl2(cod)
Pt(cod)2
PtCl2(PPh3)2
Pt(PPh3)4
HSiMe2Ph
HSiMePh2
HSiMePh2
HSiMePh2
HSiMePh2
HSiMePh2
3
18
4
3
148
30
0
1
2
3
1
0
93
94
91
89
77
78
0
0
0
0
0
0
7
5
7
8
22
22
100
98
91
95
100
100
8 d
9
10
11
12
a All reactions were run at 80°C without solvent unless otherwise noted. Initial ratio: 1:hydrosilane:catalyst=1:1.1:0.005.
b Determined by 1H-NMR spectroscopy.
c Determined by GLC using tetradecane as an internal standard.
d The reaction was conducted at 60°C.
regio- and stereoisomers of 1,2-adducts across the triple
bond. In the following sections, we describe details of
the results according to catalyst precursors and discuss
the reaction mechanisms [6].
A distinct difference in the regioselectivity depending
upon the geometry of 1 was noted for platinum-cata-
lyzed reactions (Table 1). Treatment of cis-1 with 1.1
molar ratio of HSiMe2Ph in the presence of a catalytic
amount of H2PtCl6·6H2O (0.005 molar ratio) led to
1,4-addition of hydrosilane, giving 2 in 96% selectivity
(entry 1). In contrast, the reaction of trans-1 under the
same reaction conditions gave a 1,2-adduct 3 in 93%
selectivity (entry 7). Almost the same selectivities were
observed with HSiMePh2 in place of HSiMe2Ph, al-
though the reactivity of HSiMePh2 was considerably
lower than that of HSiMe2Ph (entries 2 and 8). Plat-
inum complexes bearing 1,4-cyclooctadiene (cod) lig-
and(s) also served as selective catalysts (entries 3, 4, 9,
and 10). On the other hand, PPh3-coordinated catalysts
2. Results and discussion
2.1. Catalytic reactions
Catalytic addition of hydrosilane (HSiMe2Ph or
HSiMePh2) to cis- and trans-1 was examined at 80°C
without solvent. The reaction products were analyzed
by GLC, GC-mass spectrometry, and NMR spec-
troscopy, after removing the catalyst by column
chromatography.

132
Y. Maruyama et al. / Journal of Organometallic Chemistry 609 (2000) 130–136
afforded an 8:2 mixture of 3 and 5 irrespective of the
geometry of 1 (entries 5, 6, 11, and 12).
rhodium complexes other than RhH(CO)(PPh3)3 led to
lower selectivities (entries 2 and 6–8).
In the reactions using RuHCl(CO)(PPh3)3 as a cata-
lyst precursor, allenylsilane 2 was produced from both
isomers of 1 in high selectivities (entries 1–3 in Table
2). Predominant formation of 2 was also observed with
RuH2(CO)(PPh3)3 (entry 4), while RuH2(PPh3)4 and
RuHCl(CO)(PPri3)2 gave complicated mixtures (entries
5 and 6).
In the presence of RhH(CO)(PPh3)3 as a catalyst
precursor, cis- and trans-1 were converted into anti-
and syn-1,2-addition products 4 and 5, respectively
(Table 3). The orientation of 1,2-addition was opposite
to that observed for the platinum-catalyzed reactions of
trans-1 (see Scheme 2). The reaction of cis-1 with
HSiMe2Ph gave 4 in 95% selectivity (entry 1). On the
other hand, trans-1 was converted into 5 in 81% selec-
tivity under the same reaction conditions (entry 3). The
selectivity of 5 was improved to 93 or 96% by using
toluene as a solvent (entry 4) or by using HSiMePh2 in
place of HSiMe2Ph (entry 5), respectively. The use of
2.2. Consideration for catalytic mechanisms
The regio- and stereochemical courses of the plat-
inum- and rhodium-catalyzed reactions were clearly
dictated by the cis and trans geometries of 1. Thus, in
the reactions catalyzed by H2PtCl6·6H2O, cis- and
trans-1 gave 1,4- and 1,2-addition products of
HSiMe2Ph (2 and 3) in 96 and 93% selectivities, respec-
tively (entries 1 and 7 in Table 1). On the other hand,
in the RhH(CO)(PPh3)3-catalyzed reactions, cis- and
trans-1 underwent anti- and syn-addition of HSiMe2Ph
in 95 and 93% selectivities, respectively (entries 1 and 4
in Table 3).
Catalytic hydrosilylation is generally thought to pro-
ceed via either the Chalk–Harrod or modified Chalk–
Harrod cycle [7]. The former cycle has been commonly
assumed for platinum-catalyzed reactions [8]. On the
other hand, the latter cycle was well documented for
Table 2
Hydrosilylation of cis- and trans-1 in the presence of ruthenium catalysts a
Entry
Butenyne
Catalyst
Hydrosilane
Reaction time (h)
Product ratio b
Total yield (%) c
2
3
4
5
1
2
3
4
5
6
cis-1
RuHCl(CO)(PPh3)3
RuHCl(CO)(PPh3)3
RuHCl(CO)(PPh3)3
RuH2(CO)(PPh3)3
RuH2(PPh3)4
HSiMe2Ph
HSiMe2Ph
HSiMePh2
HSiMe2Ph
HSiMe2Ph
HSiMe2Ph
134
142
137
142
159
207
86
91
97
92
22
62
0
0
0
0
14
12
6
2
0
1
26
3
8
7
3
7
38
23
58
95
60
trans-1
trans-1
trans-1
trans-1
trans-1
92
56 d
48 d
RuHCl(CO)(PPri3)2
a All reactions were run at 80°C without solvent unless otherwise noted. Initial ratio: 1:hydrosilane:catalyst=1:1.5:0.025.
b Determined by 1H-NMR spectroscopy.
c Determined by GLC using tetradecane as an internal standard.
d Considerable amounts (30–40%) of unknown products were formed.
Table 3
Hydrosilylation of cis- and trans-1 in the presence of rhodium catalysts a
Entry
Butenyne
Catalyst
Hydrosilane
Reaction time (h)
Product ratio b
Total yield (%) c
2
3
4
5
1
2
3
cis-1
RhH(CO)(PPh3)3
RhCl(PPh3)3
RhH(CO)(PPh3)3
RhH(CO)(PPh3)3
RhH(CO)(PPh3)3
RhCl(PPh3)3
HSiMe2Ph
HSiMe2Ph
HSiMe2Ph
HSiMe2Ph
HSiMePh2
HSiMe2Ph
HSiMe2Ph
HSiMe2Ph
19
3
19
24
24
3
0
27
10
5
4
17
5
0
0
0
0
0
0
44
48
95
47
9
2
0
13
0
0
5
26
81
93
96
70
51
50
98
97
96
93
99
98
100
98
trans-1
4 d
5
6
7
8
[Rh(cod)2]BF4
[Rh(cod)(dppp)]BF4
3
3
2
a All reactions were run at 80°C without solvent unless otherwise noted. Initial ratio: 1:hydrosilane:catalyst=1:1.1;0.005.
b Determined by 1H-NMR spectroscopy.
c Determined by GLC using tetradecane as an internal standard.
d The reaction was carried out in toluene.

Y. Maruyama et al. / Journal of Organometallic Chemistry 609 (2000) 130–136
133
Scheme 3.
Group 9 metal-catalyzed systems, even when the reac-
tions were conducted with metal hydrides as catalyst
precursors [9]. Although we presently have no direct
information on the catalytic mechanisms, the alteration
of reaction product depending upon the geometry of 1
was found to be reasonably accounted for by assuming
the Chalk–Harrod and modified Chalk–Harrod cycles
for the platinum- and rhodium-catalyzed reactions, re-
spectively [10].
Our proposals for the platinum-catalyzed systems are
depicted in Scheme 3, which postulate the participation
of a common hydrido(silyl)platinum intermediate 6,
and the occurrence of the insertion of butenynes into
the PtꢁH bond of 6 according to the regiochemistries
given in Scheme 1. Thus, when the PtꢁH bond is added
to the double bond of cis-1, an h3-propargyl/allenyl
intermediate 7 will be produced (cycle I) [11]. The
subsequent CꢁSi reductive elimination that reflects the
allenyl structure 7(b) gives allenylsilane 2. When trans-1
undergoes the insertion into the PtꢁH bond at the triple
bond, an h3-butadienyl intermediate 8 is generated
(cycle II). The subsequent CꢁSi coupling at the less
hindered site of the h3-butadienyl ligand provides 3.
Scheme 4 illustrates the proposed catalytic cycles for
the rhodium systems. While the Chalk–Harrod cycles
in Scheme 3 invoke the insertion of 1 into a Pt–H
bond, the modified Chalk–Harrod cycles given in
Scheme 4 invoke the insertion into a RhꢁSi bond. Since
product 5 formed from trans-1 is a simple syn-1,2-ad-
duct, its formation may be easily interpreted by a
typical modified Chalk–Harrod process given in cycle
IV. Thus, syn-addition of a silylrhodium species 9 to
the triple bond of trans-1 gives an h3-butadienyl inter-
mediate 15. Oxidative addition of HSiMe2Ph to 15,
followed by CꢁH reductive elimination from the result-
ing 16 affords 5.
The structure of 4 derived from cis-1 indicates two
characteristic points related to the catalytic mechanism.
One is anti-addition of hydrosilane, and the other is cis
to trans isomerization of the ene part of cis-1. These
phenomena can be rationalized by the hydrosilylation
process given in cycle III. The first step is syn-addition
of a silylrhodium species 9 to the triple bond of cis-1.
This process is similar to cycle IV. However, while the
insertion complex 15 in cycle IV has a syn-p-allyl
structure, the corresponding 10 in cycle III has an
anti-p-allyl structure that causes a significant steric
repulsion between the trimethylsilyl group and the
rhodium moiety. The steric demand inherent in 10 will
be effectively reduced by its isomerization to the syn-p-
allyl isomer 13 via allenylmethyl intermediates 11 and
12. It was observed that the rhodium moiety is shifted
from the syn position to the anti position with respect
to the SiMe2Ph group during the isomerization. There-
fore, after oxidative addition of HSiMe2Ph to 13 fol-
lowed by C–H reductive elimination from 14, the
anti-addition product 4 is produced with the cis to trans
isomerization of the ene part.

134
Y. Maruyama et al. / Journal of Organometallic Chemistry 609 (2000) 130–136
3. Experimental
3.1. General procedures
HSiMe2Ph (92.3 mg, 0.678 mmol), and tetradecane
(20.5 mg, 0.103 mmol) as an internal standard for GLC
analysis. The pale yellow solution was heated at 80°C
with stirring for 3 h, giving a brown solution. At this
stage, a 100% yield of the hydrosilylation products was
obtained as confirmed by GLC. The reaction mixture
was passed through an Al2O3 column using hexane as
an eluent and concentrated under reduced pressure.
1H-NMR analysis of the resulting oily material revealed
the formation of 2 and 3 in a 96:4 ratio. Since these
isomers could not be separated from each other by
column chromatography, further purification was per-
formed by bulb-to-bulb distillation under reduced pres-
sure (95–110°C/0.1 mmHg), giving 161 mg of the
product mixture. Anal. Calc. for C18H32Si3: C, 64.98;
H, 9.69. Found: C, 64.92; H, 9.58%.
All manipulations were carried out under a nitrogen
atmosphere using conventional Schlenk techniques. Ni-
trogen gas was dried by passage through P2O5 (Merck,
SICAPENT). NMR spectra were recorded on a JEOL
JNM-A400 spectrometer (1H-NMR, 399.65 MHz; 13C-
NMR, 100.40 MHz). Chemical shifts are reported in l
ppm referred to an internal SiMe4 standard. Mass
spectra were measured with a Shimadzu QP-5000
spectrometer (EI, 70 eV). GLC analysis was performed
with a Shimadzu GC-8A instrument equipped with
a TCD detector and a Silicone OV-1 column (1 m).
The starting butenynes (cis- and trans-1) [5b,12] and
catalyst precursors (Pt(cod)2 [13], PtCl2(cod) [14],
PtCl2(PPh3)2 [15], Pt(PPh3)4 [16], RuHCl(CO)(PPh3)3
[17], RuH2(PPh3)4 [18], RuHCl(CO)(PPri3)2 [19],
RhH(CO)(PPh3)3 [20], RhCl(PPh3)3 [21], [Rh(cod)2]BF4
[22], and [Rh(cod)(dppp)]BF4 [23]) were synthesized
according to literature methods. All other compounds
were obtained from commercial sources and used with-
out purification.
All catalytic reactions reported in this paper were
similarly carried out. The structural assignments of the
products were based on the following NMR data and
NOE experiments. Analytical data for the reaction
products with HSiMePh2 (entry 8 in Table 1) was as
follows. Anal. Calc. for C23H34Si3: C, 69.98; H, 8.68.
Found: C, 70.12; H, 8.77%.
1
2a (SiMe2Ph): H-NMR (CDCl3): l −0.04 (s, 9H,
Si(CH3)3), 0.00 (s, 9H, Si(CH3)3), 0.36 (s, 6H,
SiPh(CH3)2), 1.25 (d, J=8.3 Hz, 2H, CH2), 4.38
(t, J=8.3 Hz, 1H, ꢀCH), 7.24–7.65 (m, 5H, Ph).
13C{1H}-NMR (CDCl3): l −1.7 (Si(CH3)3), −1.3
(SiPh(CH3)2), 0.1 (Si(CH3)3), 15.6 (CH2), 72.0 (ꢀCH),
86.4 (ꢀCSi), 127.5 (Ph), 128.8 (Ph), 133.9 (Ph), 139.5
3.2. Catalytic reactions
Entry 1 in Table 1 represents a typical procedure. To
a Schlenk tube containing H2PtCl6·6H2O (1.6 mg, 3.1
mmol) were added cis-1 (120 mg, 0.611 mmol),
Scheme 4.

Y. Maruyama et al. / Journal of Organometallic Chemistry 609 (2000) 130–136
135
(Ph), 213.3 (ꢀCꢀ). MS, m/z (relative intensity, %): 332
[M+, 8], 317 (1), 258 (5), 244 (33), 229 (18), 182 (26),
167 (41), 135 (100), 109 (17), 73 (81), 45 (56), 43 (48).
3a (SiMe2Ph): 1H-NMR (CDCl3): l 0.00 (s, 9H,
Si(CH3)3), 0.15 (s, 9H, Si(CH3)3), 0.38 (s, 6H,
SiPh(CH3)2), 5.69 (d, J=19.0 Hz, 1H, ꢀC(H)Si), 6.27
(s, 1H, ꢀC(H)Si), 6.88 (d, J=19.0 Hz, 1H, ꢀCH),
7.24–7.60 (m, 5H, Ph). 13C{1H}-NMR (CDCl3): l
−1.7 (SiPh(CH3)2), −1.4 (Si(CH3)3), 0.4 (Si(CH3)3),
127.6 (Ph), 128.7 (Ph), 134.0 (Ph), 134.1 (ꢀCH), 139.1
(Ph), 147.2 (ꢀCH), 148.2 (ꢀCH), 160.3 (ꢀCSi). MS, m/z
(relative intensity, %): 332 [M+, 3], 317 (1), 258 (18),
244 (38), 229 (45), 167 (58), 135 (100), 73 (99), 45 (59),
43 (54).
(relative intensity, %): 394 [M+, 1], 320 (32), 316 (25),
306 (5), 291 (8), 244 (45), 229 (34), 197 (100), 181 (8),
167 (28), 135 (34), 119 (10), 105 (14), 73 (59), 45 (39), 43
(29).
5b (SiMePh2): 1H-NMR (CDCl3): l 0.06 (s, 9H,
Si(CH3)3), 0.07 (s, 9H, Si(CH3)3), 0.67 (s, 3H,
SiPh2(CH3)), 5.86 (d, J=17.6 Hz, 1H, ꢀCH(Si)), 6.89
(d, J=10.7 Hz, 1H, ꢀCH), 6.97 (dd, J=17.6 and 10.3
Hz, 1H, ꢀCH), 7.24–7.60 (m, 10H, Ph); 13C{1H}-NMR
(CDCl3): l −2.3 (SiPh2(CH3)), −1.4 (Si(CH3)3), 1.7
(Si(CH3)3), 127.7 (Ph), 129.0 (Ph), 135.1 (Ph), 137.3
(Ph), 139.3 (ꢀCH), 142.1 (ꢀCSi(Si)), 144.4 (ꢀCH), 159.7
(ꢀCH). MS, m/z (relative intensity, %): 394 [M+, 1],
320 (35), 306 (7), 305 (9), 291 (13), 244 (32), 229 (35),
197 (55), 135 (73), 105 (15), 73 (100), 45 (38), 43 (22).
1
4a (SiMe2Ph): H-NMR (CDCl3): l −0.12 (s, 9H,
Si(CH3)3), 0.13 (s, 9H, Si(CH3)3), 0.43 (s, 6H,
SiPh(CH3)2), 5.90 (d, J=18.1 Hz, 1H, ꢀCH(Si)), 6.60
(dd, J=18.1 and 10.2 Hz, 1H, ꢀCH), 7.12 (d, J=10.7
Hz, 1H, ꢀCH), 7.45–7.60 (m, 5H). 13C{1H}-NMR
(CDCl3): l −1.6 (Si(CH3)3), 0.2 (Si(CH3)3)), 0.7
(SiPh(CH3)2)), 127.8 (Ph), 128.6 (Ph), 133.7 (Ph), 138.4
(ꢀCH), 140.9 (Ph), 143.6 (ꢀCSi(Si)), 145.1 (ꢀCH), 156.5
(ꢀCH). MS, m/z (relative intensity, %): 332 [M+, 1],
317 (1), 258 (49), 244 (42), 229 (50), 167 (46), 135 (85),
73 (100), 45 (52), 43 (44).
Acknowledgements
This work was supported by a Grant-in-Aid for
Scientific Research from the Ministry of Education,
Science, Sports and Culture, Japan.
References
5a (SiMe2Ph): 1H-NMR (CDCl3): l 0.06 (s, 9H,
Si(CH3)3), 0.10 (s, 9H, Si(CH3)3), 0.36 (s, 6H,
SiPh(CH3)2), 6.01 (d, J=18.1 Hz, 1H, ꢀCH(Si)), 6.96
(dd, J=18.1, 10.7 Hz, 1H, ꢀCH), 7.12 (d, J=10.7 Hz,
1H, ꢀCH), 7.24–7.60 (m, 5H, Ph); 13C{1H}-NMR
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(ꢀCH). MS, m/z (relative intensity, %): 332 [M+, 1],
317 (1), 258 (34), 244 (30), 229 (34), 167 (31), 135 (65),
73 (100), 45 (37), 43 (28).
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1
2b (SiMePh2): H-NMR (CDCl3): l −0.09 (s, 9H,
Si(CH3)3), −0.06 (s, 9H, Si(CH3)3), 0.63 (s, 3H,
SiPh2(CH3)), 1.15 (dd, J=14.6 and 7.8 Hz, 1H,
CH(H)), 1.22 (dd, J=14.6 and 8.8 Hz, 1H, CH(H)),
4.35 (dd, J=8.8 and 7.8 Hz, 1H, ꢀCH), 7.24–7.60 (m,
10H, Ph). 13C{1H}-NMR (CDCl3): l −1.8 (SiPh2-
(CH3)), −1.8 (Si(CH3)3), 0.1 (Si(CH3)3), 15.4 (CH2),
72.7 (ꢀCH), 84.8 (ꢀCSi), 127.5 (Ph), 129.1 (Ph), 135.0
(Ph), 137.1 (Ph), 214.9 (ꢀCꢀ). MS, m/z (relative inten-
sity, %): 394 [M+, 5], 320 (3), 306 (10), 244 (30), 229
(14), 197 (100), 182 (13), 167 (12), 135 (25), 119 (8), 105
(13), 73 (68), 45 (36), 43 (16).
1
3b (SiMePh2): H-NMR (CDCl3): l −0.04 (s, 9H,
Si(CH3)3), 0.15 (s, 9H, Si(CH3)3), 0.67 (s, 3H,
Si(CH3)Ph2), 5.68 (d, J=19.0 Hz, 1H, ꢀC(H)Si), 6.26
(s, 1H, ꢀC(H)Si), 6.96 (d, J=19 Hz, 1H, ꢀCH), 7.24–
7.60 (m, 10H, Ph). 13C{1H}-NMR (CDCl3): l −2.6
(Si(CH3)Ph2), −1.5 (Si(CH3)3), 0.4 (Si(CH3)3), 127.6
(Ph), 129.0 (Ph), 135.1 (Ph), 135.2 (ꢀCH), 136.8 (Ph),
146.9 (ꢀCH), 151.2 (ꢀCH), 158.1 (ꢀCSi). MS, m/z
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