C-Si reductive elimination from cis-vinyl(silyl)platinum(II) complexes

Article abstract of DOI:10.1021/om0580001

The complexes cis-Pt(CH=CH₂)(SiR₃)(PMe ₂Ph)₂ (SiR3 = SiPh₃ (3a), Si(C ₆H₄Me-p)₃ (3b), Si(C₆H ₄OMe-p)₃ (3c), SiMePh₂ (3d), SiFPh₂ (3e)) have been prepared by the reactions of trans-PtCl(SiR₃) (PMe₂Ph)₂ with Mg(CH=CH₂)₂ in THF, followed by trans-cis isomerization of the resulting trans-alkenyl(silyl) complexes in solution promoted by CO. Complexes 3a-e undergo C-Si reductive elimination in toluene-d₈ to give platinum(0) complexes coordinated with vinylsilanes. Kinetic data have suggested a direct reaction path without dissociation of the phosphine ligand.

Full text of DOI:10.1021/om0580001

Organometallics 2005, 24, 2511-2515
2511
C-Si Reductive Elimination from
cis-Vinyl(silyl)platinum(II) Complexes
Fumiyuki Ozawa,* Toshikazu Tani, and Hiroyuki Katayama
International Research Center for Elements Science, Institute for Chemical Research, Kyoto
University, Uji, Kyoto 611-0011, Japan
Received January 5, 2005
The complexes cis-Pt(CHdCH2)(SiR3)(PMe2Ph)2 (SiR3 ) SiPh3 (3a), Si(C6H4Me-p)3 (3b),
Si(C6H4OMe-p)3 (3c), SiMePh2 (3d), SiFPh2 (3e)) have been prepared by the reactions of
trans-PtCl(SiR3)(PMe2Ph)2 with Mg(CHdCH2)2 in THF, followed by trans-cis isomerization
of the resulting trans-alkenyl(silyl) complexes in solution promoted by CO. Complexes 3a-e
undergo C-Si reductive elimination in toluene-d8 to give platinum(0) complexes coordinated
with vinylsilanes. Kinetic data have suggested a direct reaction path without dissociation
of the phosphine ligand.
Introduction
Me > Et > Pr > Bu.4c Although this order is the opposite
of that commonly observed for C-C reductive elimina-
tion from group 10 metal alkyls, a recent theoretical
study has suggested that a longer alkyl group causes
higher steric repulsion between the alkyl and silyl
ligands in the transition state, leading to a higher
activation barrier for C-Si reductive elimination.3a On
the other hand, reductive elimination from cis-Pt(Ct
CAr)(SiR3)L2 type complexes bearing sp-hybridized
alkynyl ligands proceeds directly from the four-coordi-
nate species without dissociation of L.4a In this case,
more electron-donating alkynyl and silyl ligands provide
higher reductive elimination rates.
While the transition-metal-catalyzed silylation reac-
tions of unsaturated hydrocarbons such as hydrosily-
lation, bis-silylation, and borylsilylation are generally
assumed to involve C-Si reductive elimination as the
product-forming step,1 detailed information on this
elementary process has been limited.2-4 We have ex-
amined mechanisms of reductive elimination from cis-
PtR′(SiR3)L2 type complexes (R′ ) alkyl, aryl, alkynyl;
L ) PMe2Ph) in solution.4 Two types of mechanisms
have been observed, depending on hybridization of the
carbyl ligands (R′). When R′ is an alkyl group having
an sp3-hybridized carbon, the reductive elimination is
a very slow process in neat solvents but is effectively
accelerated by addition of diphenylacetylene to the
system.4e,f The product alkylsilanes are eliminated from
[PtR′(SiR3)(PhCtCPh)L] intermediates formed by ligand
exchange of L with diphenylacetylene. The reaction
rates decrease according to the alkyl ligands in the order
This paper reports the synthesis and thermolysis
behavior of cis-Pt(CHdCH2)(SiR3)L2 type complexes.
These complexes bearing sp2-hybridized ligands possess
much higher reactivity than the alkyl and alkynyl
analogues. The reductive elimination takes place di-
rectly from the four-coordinate species.
(1) (a) Suginome, M.; Ito, Y. Chem. Rev. 2000, 100, 3221. (b)
Beletskaya, I.; Moberg, C. Chem. Rev. 1999, 99, 3435. (c) Corey, J. Y.;
Braddock-Wilking, J. Chem. Rev. 1999, 99, 175. (d) Braunstein, P.;
Knorr, M. J. Organomet. Chem. 1995, 500, 21.
Results and Discussion
Synthesis of cis-Pt(CHdCH2)(SiR3)(PMe2Ph)2
(3a-e). cis-Alkyl(silyl) analogues of the title compounds
have been synthesized in one pot by the treatment of
trans-PtCl(SiR3)L2 with an excess amount of alkyl-
lithium (R′Li), followed by methanolysis of the resulting
Li+[Pt(R′)2(SiR3)L]- species.4f However, similar reac-
tions using vinyllithium instead of alkyllithium provided
complex mixtures. Accordingly, 3a-e were synthesized
by the two-step procedure shown in Scheme 1. The
reactions of 1a-e with divinylmagnesium took place
instantly at room temperature to give trans complexes
2a-e, which were isolated as analytically pure solids
in 46-68% yields by recrystallization. Treatment of
2a-e with CO in solution at low temperature resulted
in trans-cis isomerization to give 3a-e in quantitative
yields. Since 3a-e were too unstable to be isolated, they
were characterized by NMR spectroscopy.
(2) (a) Roy, A. K.; Taylor, R. B. J. Am. Chem. Soc. 2002, 124, 9510.
(b) Maruyama, Y.; Yamamura, K.; Sagawa, T.; Katayama, H.; Ozawa,
F. Organometallics 2000, 19, 1308. (c) van der Boom, M. E.; Ott, J.;
Milstein, D. Organometallics 1998, 17, 4263. (d) Tanaka, Y.; Ya-
mashita, H.; Shimada, S.; Tanaka, M. Organometallics 1997, 16, 3246.
(e) Okazaki, M.; Tobita, H.; Ogino, H. Organometallics 1996, 15, 2790.
(f) Mitchell, G. P.; Tilley, T. D. Organometallics 1996, 15, 3477. (g)
Aizenberg, M.; Milstein, D. J. Am. Chem. Soc. 1995, 117, 6456. (h)
Schubert, U. Angew. Chem., Int. Ed. 1994, 33, 419. (i) Lin, W.; Wilson,
S. R.; Girolami, G. S. Organometallics 1994, 13, 2309. (j) Schubert,
U.; Mu¨ller, C. J. Organomet. Chem. 1989, 373, 165. (k) Brinkman, K.
C.; Blakeney, A. J.; Krone-Schmidt, W.; Gladysz, J. A. Organometallics
1984, 3, 1325.
(3) (a) Sakurai, H.; Sugimoto, M. J. Organomet. Chem. 2004, 689,
2236. (b) Beste, A.; Frenking, G. Z. Anorg. Allg. Chem. 2000, 626, 381.
(c) Biswas, B.; Sugimoto, M.; Sakaki, S. Organometallics 1999, 18,
4015. (d) Sakaki, S.; Mizoe, N.; Sugimoto, M. Organometallics 1998,
17, 2510. (e) Sakaki, S.; Mizoe, N.; Musashi, Y.; Sugimoto, M. J. Phys.
Chem. A 1998, 102, 8027.
(4) (a) Ozawa, F.; Mori, T. Organometallics 2003, 22, 3593. (b)
Ozawa, F. J. Organomet. Chem. 2000, 611, 332. (c) Hasebe, K.; Kamite,
J.; Mori, T.; Katayama, H.; Ozawa, F. Organometallics 2000, 19, 2022.
(d) Ozawa, F.; Kitaguchi, M.; Katayama, H. Chem. Lett. 1999, 1289.
(e) Ozawa, F.; Hikida, T.; Hasebe, K.; Mori, T. Organometallics 1998,
17, 1018. (f) Ozawa, F.; Hikida, T.; Hayashi, T. J. Am. Chem. Soc. 1994,
116, 2844.
The trans isomers 2a-e exhibited a singlet signal
with 195Pt satellites in the 31P{1H} NMR spectra; the
1JPtP values (2681-2790 Hz) were typical of platinum-
10.1021/om0580001 CCC: $30.25 © 2005 American Chemical Society
Publication on Web 04/13/2005

2512 Organometallics, Vol. 24, No. 10, 2005
Ozawa et al.
Table 1. First-Order Rate Constants for Reductive
Scheme 1
Elimination from 3a-ea
run complex
SiR3
CHdCHR′ temp (°C) 103k (s-1
)
1
2b
3
4
5
6
7
8
9
3a
3a
3a
3a
3a
3b
3c
3d
3e
SiPh3
SiPh3
SiPh3
SiPh3
SiPh3
CHdCH2
CHdCH2
CHdCH2
CHdCH2
CHdCH2
CHdCH2
CHdCH2
CHdCH2
CHdCH2
25.0
25.0
20.0
15.0
10.0
10.0
10.0
10.0
10.0
1.20(10)
1.21(9)
0.633(5)
0.354(4)
0.188(2)
0.352(4)
0.403(3)
0.144(1)
0.141(1)
c
SiAr3
d
SiAr′3
SiMePh2
SiFPh2
a Conditions: in toluene-d8, [complex]0 ) 30 mM. b The reaction
was examined in the presence of PMe2Ph (30 mM). c Ar )
p-MeC6H4. d Ar′ ) p-MeOC6H4.
occurrence of a direct reductive elimination process
without prior dissociation of PMe2Ph (runs 1 and 2).
Activation parameters estimated for a temperature
range of 10.0-25.0 °C (runs 1-5) are as follows: ∆Hq
) 20.0(4) kcal mol-1, ∆Sq ) -5(1) eu, ∆Gq ) 21.5(4) kcal
mol-1. The activation energy (∆Gq) for 3a is smaller than
that previously observed for related methyl(silyl) and
phenylethynyl(silyl) complexes: PtMe(SiPh3)(PhCtCPh)-
(PMe2Ph) (22.8 kcal mol-1) and cis-Pt(CtCPh)(SiPh3)-
(PMe2Ph)2 (23.2 kcal mol-1).5
Reductive elimination rates decreased according to
silyl ligands in the order 3c (Si(C6H4OMe-p)3) > 3b (Si-
(C6H4Me-p)3) > 3a (SiPh3) > 3d (SiMePh2) ≈ 3e
(SiFPh2) (runs 5-9). While the rate variation is small,
the observed tendency suggests that the reactivity of
vinyl(silyl)platinum complexes toward C-Si reductive
elimination is dependent on the bulkiness of the silyl
ligands. Thus, 3d,e, having sterically similar but elec-
tronically different silyl ligands (i.e., SiMePh2 and
SiFPh2), give almost the same reaction rates, and these
complexes are less reactive than 3a-c bearing bulkier
silyl ligands. It is possible that steric repulsion between
triarylsilyl ligands and PMe2Ph ligands in 3a-c facili-
tates the approach of the silyl ligand to the vinyl ligand
during C-Si reductive elimination to cause the higher
reaction rates. A similar phenomenon has been reported
for C-C reductive elimination from group 10 metal
complexes.6 On the other hand, for 3a-c having triar-
ylsilyl ligands with almost the same sizes, the reductive
elimination rate increases as the electron-donating
ability of the aryl group increases (runs 5-7). A similar
tendency has been observed for cis-Pt(CtCPh)(SiR3)-
(PMe2Ph)2 complexes (SiR3 ) SiPh3, Si(C6H4Me-p)3, Si-
(C6H4OMe-p)3, Si(C6H4CF3-p)3).4a
(II) complexes coordinated with two phosphine ligands
in mutually trans positions. The cis isomers 3a-e
exhibited two sets of doublets, reflecting the cis-bis-
(phosphine)platinum(II) structures with two additional
ligands. One of the doublets involved 1JPtP couplings of
1988-2002 Hz, and this signal was assigned to the
phosphine trans to the vinyl ligand. On the other hand,
owing to the strong trans influence of silyl ligands, 1JPtP
couplings observed for the other doublet were signifi-
cantly smaller (1290-1382 Hz).
In the 13C{1H} NMR spectra, R- and â-vinylic carbon
signals of trans isomers were observed, each being a
triplet owing to the couplings with two equivalent
phosphorus nuclei. On the other hand, R- and â-vinylic
carbons of cis isomers exhibited doublet of doublets and
doublet signals, respectively. The R-carbon involved
large and small 2JPC couplings (89-96 and 15-17 Hz),
consistent with trans and cis arrangements of phosphine
ligands toward the vinyl ligand.
Reductive Elimination Reactions. The cis-vinyl-
(silyl) complexes 3a-e underwent C-Si reductive elimi-
nation in solution to give platinum(0) complexes coor-
dinated with vinylsilanes (4a-e) (Scheme 1). For
example, when the reaction of 3a in toluene-d8 was
followed by 31P{1H} NMR spectroscopy at 10 °C, the
signals of 3a at δ -13.7 and -5.2 gradually decreased
over a period of several hours and were replaced by two
sets of doublets at δ -6.7 (d, 2JPP ) 49 Hz, 1JPtP ) 3538
2
1
Hz) and -7.6 (d, JPP ) 49 Hz, JPtP ) 3581 Hz). The
1JPtP values thus observed were larger than those of 3a
(1990 and 1347 Hz), consistent with a platinum(0)
complex. In the 13C{1H} NMR spectrum, vinylic carbon
Conclusion. The C-Si reductive elimination from
cis-Pt(CHdCH2)(SiR3)(PMe2Ph)2 complexes (3a-e) has
been found to take place directly from the four-
coordinate species, as already found for cis-alkynyl(silyl)
analogues.4a The reactivity is affected by both the
signals appeared as two sets of doublet of doublets with
1
195Pt satellites at δ 27.3 (2JPC ) 29 and 4 Hz, JPtC
)
216 Hz) and 35.2 (2JPC ) 32 and 4 Hz, 1JPtC ) 211 Hz);
the chemical shifts were significantly higher than those
of 3a (δ 117.6 and 158.7), showing the formation of the
vinylsilane-coordinated complex 4a. The reactions of
3b-e proceeded similarly. All reactions obeyed first-
order kinetics over 2 half-lives, giving 4a-e quantita-
tively.
(5) Kinetic parameters are as follows. PtMe(SiPh3)(PhCtCPh)(PMe2-
Ph): ∆Hq ) 20.8 kcal mol-1, ∆Sq ) -6.8 eu, ∆Gq ) 22.8 kcal mol-1, k
) 0.45 × 10-3 s-1 at 35 °C. cis-Pt(CtCPh)(SiPh3)(PMe2Ph)2: ∆Hq
s-1 at 35 °C.
)
26.4 kcal mol-1, ∆Sq ) 10 eu, ∆Gq ) 23.2 kcal mol-1, k ) 0.283 × 10-3
(6) (a) Marcone, J. E.; Moloy, K. G. J. Am. Chem. Soc. 1998, 120,
8527. (b) Mann, G.; Baranano, D.; Hartwig, J. F.; Rheingold, A. L.;
Guzei, I. A. J. Am. Chem. Soc. 1998, 120, 9205. (c) Hayashi, T.; Konishi,
M.; Kobori, Y.; Kumada, M.; Higuchi, T.; Hitotsu, K. J. Am. Chem.
Soc. 1984, 106, 158. (d) Kohara, T.; Yamamoto, T.; Yamamoto, A. J.
Organomet. Chem. 1980, 192, 265. (e) Ozawa, F. In Current Methods
in Inorganic Chemistry. 3. Fundamentals of Molecular Catalysis;
Kurosawa, H., Yamamoto, A., Eds.; Elsevier Science: Amsterdam,
2003; p 479.
Rate constants for the reductive elimination from 3a
measured under several conditions are listed in runs
1-5 in Table 1. Unlike the reactions of cis-alkyl(silyl)
analogues, the reaction of 3a is not retarded by addition
of free PMe2Ph (1 equiv) to the system, showing the

cis-Vinyl(silyl)platinum(II) Complexes
Organometallics, Vol. 24, No. 10, 2005 2513
2c (46% yield). 1H NMR (CD2Cl2, 20 °C): δ 1.36 (virtual
electronic and steric factors of silyl ligands. Thus, the
reaction proceeds more rapidly when the silyl ligand is
bulkier. For the triarylsilyl complexes 3a-c, more
electron-donating groups provide higher reductive elimi-
nation rates.
3
triplet, J ) 3.4 Hz, JPtH ) 32.2 Hz, 12H, PMe), 3.75 (s, 9H,
3
2
4
OMe), 5.18 (ddt, JHH ) 20.0 Hz, JHH ) 3.9 Hz, JPH ) 2.0
3
3
Hz, JPtH ) 43.9 Hz, 1H, PtCHdCH2), 6.16 (ddt, JHH ) 13.1
Hz, 2JHH ) 3.9 Hz, 4JPH ) 2.0 Hz, 3JPtH ) 86.4 Hz, 1H, PtCHd
CH2), 6.69 (d, 3JHH ) 8.7 Hz, 6H, Ar), 7.1-7.4 (m, 7H, Ph and
PtCHdCH2), 7.43 (d, 3JHH ) 8.7 Hz, 6H, Ar), 7.52 (m, 4H, Ph).
13C{1H} NMR (CD2Cl2, 20 °C): δ 15.1 (virtual triplet, J ) 20
Experimental Section
2
Hz, JPtC ) 40 Hz, PMe), 55.2 (s, OMe), 112.8 (s, SiAr), 123.1
All manipulations were carried out under a nitrogen atmo-
sphere using conventional Schlenk techniques. NMR spectra
were recorded on a Varian Mercury 300 spectrometer. Chemi-
cal shifts are reported in δ (ppm), referenced to the 1H (of
residual protons) and 13C signals of the deuterated solvents
or to the 31P and 195Pt signals of external H3PO4 and K2PtCl6
standards. An ethereal solution of Mg(CHdCH2)2 was prepared
by the treatment of Mg(CHdCH2)Cl with dioxane in Et2O,
followed by removal of the resulting precipitate of MgCl2-
(dioxane) by filtration. Elemental analysis was performed on
a Perkin-Elmer 2400II CHN Analyzer. The complexes trans-
PtCl(SiR3)(PMe2Ph)2 (1a-e) were prepared according to lit-
erature procedures.7
3
(t, JPC ) 4 Hz, PtCHdCH2), 128.2 (virtual triplet, J ) 5 Hz,
3
PPh), 129.6 (s, PPh), 131.8 (virtual triplet, J ) 6 Hz, JPtC
)
24 Hz, PPh), 137.1 (virtual triplet, J ) 28 Hz, PPh), 138.3 (s,
3JPtC ) 16 Hz, SiAr), 139.3 (t, 3JPC ) 2 Hz, 2JPtC ) 28 Hz, SiAr),
159.2 (s, SiAr), 172.6 (t, 2JPC ) 14 Hz, 1JPtC ) 511 Hz, PtCHd
1
CH2). 31P{1H} NMR (CD2Cl2, 20 °C): δ -8.7 (s, JPtP ) 2775
Hz). Anal. Calcd for C39H46O3P2PtSi: C, 55.25; H, 5.47.
Found: C, 55.01; H, 5.47.
2d (58% yield). 1H NMR (CD2Cl2, 20 °C): δ 0.33 (s, 3JPtH
)
)
3
15.0 Hz, 3H, SiMe), 1.47 (virtual triplet, J ) 3.6 Hz, JPtH
32.4 Hz, 12H, PMe), 5.11 (ddt, 3JHH ) 19.8 Hz, 2JHH ) 3.6 Hz,
3
4JPH ) 2.1 Hz, JPtH ) 44.4 Hz, 1H, PtCHdCH2), 6.13 (ddt,
3JHH ) 13.2 Hz, 2JHH ) 3.9 Hz, 4JPH ) 1.8 Hz, 3JPtH ) 85.8 Hz,
1H, PtCHdCH2), 7.0-7.7 (m, 21H, Ph and PtCHdCH2). 13C-
Preparation of trans-Pt(CHdCH2)(SiPh3)(PMe2Ph)2
(2a). To a solution of trans-PtCl(SiPh3)(PMe2Ph)2 (1a; 800 mg,
1.04 mmol) in THF (15 mL) was added a solution of Mg(CHd
CH2)2 in Et2O (0.86 M, 1.3 mL, 1.12 mmol). The mixture was
stirred for 30 min at room temperature and then cooled to -30
°C. Methanol (1 mL) was slowly added, and the solution was
concentrated to dryness under vacuum. The resulting solid was
extracted with benzene (5 mL × 2), filtered through a Celite
pad to remove magnesium salts, and concentrated to dryness
to give a yellow solid, which was washed with hexane contain-
ing a small amount of Et2O and dried under vacuum. The
crude product was dissolved in a minimum amount of CH2-
Cl2, layered with hexane, and allowed to stand at -70 °C to
give colorless crystals of 2a (536 mg, 68%). Complexes 2b-e
were similarly prepared.
{1H} NMR (CD2Cl2, 20 °C): δ 4.4 (virtual triplet, J ) 2 Hz,
2
2JPtC ) 38 Hz, SiMe), 15.5 (virtual triplet, J ) 20 Hz, JPtC
)
3
40 Hz, PMe), 122.8 (t, JPC ) 4 Hz, PtCHdCH2), 126.7 (s,
SiPh), 127.2 (s, SiPh), 128.3 (virtual triplet, J ) 5 Hz, PPh),
129.8 (s, PPh), 131.8 (virtual triplet, J ) 6 Hz, 3JPtC ) 25 Hz,
PPh), 135.7 (s, 3JPtC ) 14 Hz, SiPh), 137.1 (virtual triplet, J )
28 Hz, PPh), 150.8 (s, 3JPC ) 2 Hz, 2JPtC ) 26 Hz, SiPh), 172.7
2
1
(t, JPC ) 14 Hz, JPtC ) 509 Hz, PtCHdCH2). 31P{1H} NMR
1
(CD2Cl2, 20 °C): δ -7.6 (s, JPtP ) 2790 Hz). Anal. Calcd for
C31H38P2PtSi: C, 53.52; H, 5.51. Found: C, 53.29; H, 5.56.
2e (51% yield). 1H NMR (CD2Cl2, 20 °C): δ 1.59 (virtual
triplet, J ) 3.6 Hz, 3JPtH ) 33.0 Hz, 12H, PMe), 4.49 (m, 3JHH
2
3
) 20.1 Hz, JHH ) 4.0 Hz, JPtH ) 43.8 Hz, 1H, PtCHdCH2),
6.10 (dddt, 3JHH ) 13.2 Hz, 2JHH ) 3.9 Hz, 4JFH ) 2.0 Hz, 4JPH
) 2.0 Hz, 3JPtH ) 85.2 Hz, 1H, PtCHdCH2), 7.2-7.4 (m, 13 H,
Ph and PtCHdCH2), 7.4-7.6 (m, 8H, Ph). 13C{1H} NMR (CD2-
2a. 1H NMR (CD2Cl2, 20 °C): δ 1.34 (virtual triplet, J ) 3.3
3
3
Hz, JPtH ) 32.1 Hz, 12H, PMe), 5.17 (ddt, JHH ) 19.8 Hz,
2JHH ) 3.9 Hz, JPH ) 2.1 Hz, JPtH ) 44.4 Hz, 1H, PtCHd
CH2), 6.15 (ddt, 3JHH ) 12.6 Hz, 2JHH ) 3.9 Hz, 4JPH ) 2.1 Hz,
3JPtH ) 87.3 Hz, 1H, PtCHdCH2), 7.1-7.6 (m, 26H, Ph and
PtCHdCH2). 13C{1H} NMR (CD2Cl2, 20 °C): δ 15.2 (virtual
triplet, J ) 20 Hz, 2JPtC ) 40 Hz, PMe), 123.3 (t, 3JPC ) 4 Hz,
PtCHdCH2), 127.2 (s, SiPh), 127.3 (s, SiPh), 128.4 (virtual
triplet, J ) 5 Hz, PPh), 129.9 (s, PPh), 131.9 (virtual triplet,
4
3
2
Cl2, 20 °C): δ 15.8 (virtual triplet, J ) 21 Hz, JPtC ) 40 Hz,
PMe), 123.7 (t, 3JPC ) 4 Hz, PtCHdCH2), 127.5 (s, SiPh), 128.2
(s, SiPh), 128.3 (virtual triplet, J ) 5 Hz, PPh), 129.9 (s, PPh),
131.7 (virtual triplet, J ) 6 Hz, 3JPtC ) 23 Hz, PPh), 135.4 (d,
3
3JFC ) 2 Hz, JPtC ) 14 Hz, SiPh), 136.2 (virtual triplet, J )
28 Hz, PPh), 147.6 (d, 2JFC ) 16 Hz, 2JPtC ) 28 Hz, SiPh), 172.0
(td, 2JPC ) 14 Hz, 3JFC ) 12 Hz, 1JPtC ) 508 Hz, PtCHdCH2).
3
J ) 5 Hz, JPtC ) 23 Hz, PPh), 137.0 (virtual triplet, J ) 28
3
1
31P{1H} NMR (CD2Cl2, 20 °C): δ -7.6 (d, JFC ) 10 Hz, JPtP
) 2681 Hz). Anal. Calcd for C30H35FP2PtSi: C, 51.50; H, 5.04.
Found: C, 51.50; H, 5.47.
3
2
Hz, PPh), 137.5 (s, JPtC ) 16 Hz, SiPh), 148.3 (s, JPtC ) 25
Hz, SiPh), 171.8 (t, 2JPC ) 13 Hz, 1JPtC ) 512 Hz, PtCHdCH2).
31P{1H} NMR (CD2Cl2, 20 °C): δ -9.2 (s, JPtP ) 2756 Hz).
1
Generation and Characterization of cis-Pt(CHdCH2)-
(SiPh3)(PMe2Ph)2 (2a). Complex 2a (50 mg, 66 µmol) was
dissolved in CD2Cl2 (1.0 mL) in a 25 mL Schlenk flask. The
reaction mixture was evacuated, placed under CO (1 atm) at
-70 °C, and stirred at -30 °C for 1 h. The CO gas was removed
at -70 °C under vacuum, and then N2 was introduced. A part
of the solution (ca. 0.6 mL) was transferred into an NMR
sample tube equipped with a rubber septum cap and examined
by NMR spectroscopy at -30 °C, showing complete conversion
of 2a to 3a. A similar procedure was used to generate 3b-e.
Complexes 3a-e were too unstable to be isolated and were
Anal. Calcd for C36H40P2PtSi: C, 57.06; H, 5.32. Found: C,
56.97; H, 5.32.
2b (54% yield). 1H NMR (CD2Cl2, 20 °C): δ 1.33 (virtual
3
triplet, J ) 3.6 Hz, JPtH ) 32.1 Hz, 12H, PMe), 2.27 (s, 9H,
3
2
4
Me), 5.14 (ddt, JHH ) 19.8 Hz, JHH ) 4.0 Hz, JPH ) 1.8 Hz,
3JPtH ) 43.8 Hz, 1H, PtCHdCH2), 6.12 (ddt, JHH ) 12.9 Hz,
3
4
3
2JHH ) 4.0 Hz, JPH ) 2.1 Hz, JPtH ) 86.4 Hz, 1H, PtCHd
3
CH2), 6.92 (d, JHH ) 7.8 Hz, 6H, Ar), 7.0-7.5 (m, 11H, Ph
and PtCHdCH2), 7.41 (d, 3JHH ) 7.8 Hz, 6H, Ar). 13C{1H} NMR
2
(CD2Cl2, 20 °C): δ 15.0 (virtual triplet, J ) 20 Hz, JPtC ) 40
3
Hz, PMe), 21.3 (s, Me), 123.0 (t, JPC ) 4 Hz, PtCHdCH2),
1
identified by H, 31C{1H}, 31P{1H}, and 195Pt{1H} NMR spec-
127.9 (s, SiAr), 128.1 (virtual triplet, J ) 5 Hz, PPh), 129.5 (s,
troscopy.
3
PPh), 131.7 (virtual triplet, J ) 6 Hz, JPtC ) 24 Hz, PPh),
3
3a. 1H NMR (CD2Cl2, -30 °C): δ 0.97 (d, JPH ) 8.3 Hz,
136.5 (s, SiAr), 137.0 (virtual triplet, J ) 30 Hz, PPh), 137.2
2JPtH ) 22.4 Hz, 6H, PMe), 1.32 (d, 2JPH ) 8.0 Hz, 3JPtH ) 17.6
Hz, 6H, PMe), 4.90 (dddd, 3JHH ) 19.5 Hz, 2JHH ) 4.4 Hz, 4JPH
) 8.8 and 4.4 Hz, 3JPtH ) 72.2 Hz, 1H, PtCHdCH2), 5.63 (dddd,
3
3
2
(s, JPtC ) 16 Hz, SiAr), 144.6 (t, JPC ) 2 Hz, JPtC ) 23 Hz,
2
1
SiAr), 172.4 (t, JPC ) 14 Hz, JPtC ) 511 Hz, PtCHdCH2).
31P{1H} NMR (CD2Cl2, 20 °C): δ -9.2 (s, JPtP ) 2771 Hz).
1
3JHH ) 12.7 Hz, JHH ) 4.4 Hz, JPH ) 18.1 and 3.9 Hz, JPtH
2
4
3
Anal. Calcd for C39H46P2PtSi: C, 58.56; H, 5.80. Found: C,
58.66; H, 5.80.
) 130.8 Hz, 1H, PtCHdCH2), 7.02 (m, 1H, PtCHdCH2), 7.25-
7.45 (m, 19H, Ph), 7.73 (d, JHH ) 6.3 Hz, 6H, Ph). 13C{1H}
3
1
2
NMR (CD2Cl2, -30 °C): δ 12.2 (d, JPC ) 26 Hz, JPtC ) 26
(7) Chatt, J.; Eaborn, C.; Ibekwe, S. D.; Kapoor, P. N. J. Chem. Soc.
A 1970, 1343.
Hz, PMe), 16.1 (dd, 1JPC ) 24 Hz, 3JPC ) 5 Hz, 2JPtC ) 30 Hz,

2514 Organometallics, Vol. 24, No. 10, 2005
Ozawa et al.
PMe), 117.6 (d, 3JPC ) 8 Hz, 2JPtC ) 20 Hz, PtCHdCH2), 126.8
δ -13.0 (d, 2JPP ) 18 Hz, 1JPtP ) 2002 Hz), -5.6 (d, 2JPP ) 18
3
1
(s, SiPh), 127.0 (s, SiPh), 128.1 (d, JPC ) 8 Hz, PPh), 128.4
Hz, JPtP ) 1292 Hz). 195Pt{1H} NMR (CD2Cl2, -30 °C): δ
3
1
1
(d, JPC ) 10 Hz, PPh), 129.2 (s, PPh), 129.6 (s, PPh), 130.7
-4828 (dd, JPPt ) 2004 and 1294 Hz, JPtSi ) 1324 Hz).
(d, 2JPC ) 10 Hz, PPh), 130.8 (d, 2JPC ) 12 Hz, PPh), 137.1 (s,
3e. 1H NMR (CD2Cl2, -30 °C): δ l.36 (d, 3JPH ) 8.1 Hz, 2JPtH
1
2JPtC ) 21 Hz, SiPh), 137.5 (d, JPC ) 34 Hz, PPh), 139.4 (dd,
) 18.0 Hz, 6H, PMe), 1.65 (d, JPH ) 8.7 Hz, 2JPtH ) 25.5 Hz,
3
3
3
2
1JPC ) 43 Hz, JPC ) 3 Hz, PPh), 145.0 (d, JPC ) 3 Hz, JPtC
3
2
4
6H, PMe), 4.94 (dddd, JHH ) 19.5 Hz, JHH ) 4.5 Hz, JPH
)
2
1
8.4 and 4.5 Hz, 3JPtH ) 70.8 Hz, 1H, PtCHdCH2), 6.12 (dddd,
) 50 Hz, SiPh), 158.7 (dd, JPC ) 94 and 15 Hz, JPtC ) 672
Hz, PtCHdCH2). 31P{1H} NMR (CD2Cl2, -30 °C): δ -13.7 (d,
3JHH ) 12.9 Hz, JHH ) 4.5 Hz, JPH ) 16.5 and 4.5 Hz, JPtH
) 133.8 Hz, 1H, PtCHdCH2), 7.16 (m, 1H, PtCHdCH2), 7.25-
7.7 (m, 20 H, Ph). 13C{1H} NMR (CD2Cl2, -30 °C): δ 12.9 (dd,
2
4
3
2JPP ) 20 Hz, 1JPtP ) 1988 Hz), -5.2 (d, 2JPP ) 20 Hz, 1JPtP
)
1342 Hz, 2JSiP ) 180 Hz). 195Pt{1H} NMR (CD2Cl2, -30 °C): δ
1
1
1JPC ) 27 Hz, JFC ) 2 Hz, JPtC ) 26 Hz, PMe), 17.8 (ddd,
4
2
-4821 (dd, JPPt ) 1990 and 1347 Hz, JPtSi ) 1408 Hz).
1JPC ) 32 Hz, JPC ) 4 Hz, JFC ) 4 Hz, JPtC ) 39 Hz, PMe),
3
4
2
3b. 1H NMR (CD2Cl2, -30 °C): δ 0.94 (d, JPH ) 8.4 Hz,
3
3
2
2JPtH ) 22.2 Hz, 6H, PMe), 1.28 (d, 3JPH ) 8.1 Hz, 2JPtH ) 17.4
123.2 (d, JPC ) 7 Hz, JPtC ) 27 Hz, PtCHdCH2), 127.1 (s,
3
3
SiPh), 128.0 (s, SiPh), 128.2 (d, JPC ) 9 Hz, PPh), 128.4 (d,
Hz, 6H, PMe), 2.29 (s, 9H, Me), 4.89 (dddd, JHH ) 19.8 Hz,
3JPC ) 10 Hz, PPh), 129.5 (s, PPh), 129.6 (s, PPh), 130.5 (d,
2JHH ) 4.5 Hz, JPH ) 8.4 and 4.2 Hz, JPtH ) 72.6 Hz, 1H,
4
3
2JPC ) 12 Hz, PPh), 130.7 (d, JPC ) 11 Hz, PPh), 135.5 (d,
2
3
2
4
PtCHdCH2), 5.61 (dddd, JHH ) 13.2 Hz, JHH ) 4.5 Hz, JPH
3JFC ) 2 Hz, 2JPtC ) 15 Hz, SiPh), 137.4 (d, 1JPC ) 35 Hz, PPh),
3
) 17.7 and 4.2 Hz, JPtH ) 132.6 Hz, 1H, PtCHdCH2), 6.94
1
3
2
(m, 1H, PtCHdCH2), 7.06 (d, 3JHH ) 7.8 Hz, 6H, Ar), 7.0-7.5
138.9 (dd, JPC ) 45 Hz, JPC ) 4 Hz, PPh), 143.6 (dd, JFC
)
)
3
2
2
(m, 10H, Ph), 7.55 (d, JHH ) 7.8 Hz, 6H, Ar). 13C{1H} NMR
3
16 Hz, JPC ) 10 Hz, JPtC ) 100 Hz, SiPh), 154.4 (dd, JPC
89 and 15 Hz, 1JPtC ) 652 Hz, PtCHdCH2). 31P{1H} NMR (CD2-
(CD2Cl2, -30 °C): δ 11.8 (d, 1JPC ) 27 Hz, 2JPtC ) 25 Hz, PMe),
15.7 (dd, 1JPC ) 28 Hz, 3JPC ) 4 Hz, 2JPtC ) 30 Hz, PMe), 21.2
2
3
1
Cl2, -30 °C): δ -8.0 (dd, JPP ) 20 Hz, JFP ) 21 Hz, JPtP
)
2
3
1
3
1994 Hz), -5.0 (dd, JPP ) 20 Hz, JFP ) 57 Hz, JPtP ) 1382
(s, Me), 116.8 (d, JPC ) 9 Hz, PtCHdCH2), 127.5 (s, SiAr),
Hz). 195Pt{1H} NMR (CD2Cl2, -30 °C): δ -4729 (ddd, JPPt
)
1
127.9 (d, 3JPC ) 9 Hz, PPh), 128.0 (d, 3JPC ) 10 Hz, PPh), 128.9
2
1
2
2004 and 1397 Hz, JFPt ) 379 Hz, JPtSi ) 1512 Hz).
(s, PPh), 129.4 (s, PPh), 130.4 (d, JPC ) 10 Hz, PPh), 130.6
(d, 2JPC ) 11 Hz, PPh), 136.4 (s, SiAr), 136.9 (s, 2JPtC ) 21 Hz,
Kinetic Experiments. A typical procedure is as follows.
Complex 2a (22.7 mg, 30.0 µmol) was placed in a Schlenk tube
and dissolved in toluene-d8 (1.0 mL) at room temperature. The
system was evacuated at -70 °C and filled with CO (1 atm),
and the mixture was stirred at -30 °C for 1 h to produce 3a.
The CO gas was removed at -70 °C under vacuum and
replaced with N2 gas (1 atm). A part of the solution (ca. 0.6
mL) was transferred into an NMR sample tube equipped with
a rubber septum cap. The amounts of 3a and 4a at intervals
were determined by 31P{1H} NMR spectroscopy. The conver-
sion of 3a to 4a proceeded quantitatively without any notable
side reaction. All kinetic runs given in Table 1 were similarly
1
1
SiAr), 137.4 (d, JPtC ) 35 Hz, PPh), 139.5 (dd, JPC ) 44 Hz,
3JPC ) 5 Hz, PPh), 141.3 (dd, 3JPC ) 6 and 2 Hz, 1JPC ) 54 Hz,
SiAr), 159.4 (dd, 2JPC ) 94 and 17 Hz, 1JPtC ) 668 Hz, PtCHd
CH2). 31P{1H} NMR (CD2Cl2, -30 °C): δ -14.6 (d, JPP ) 21
2
Hz, 1JPtP ) 1995 Hz), -5.7 (d, 2JPP ) 21 Hz, 1JPtP ) 1313 Hz).
195Pt{1H} NMR (CD2Cl2, -30 °C): δ -4763 (dd, JPPt ) 2003
1
1
and 1316 Hz, JPtSi ) 1395 Hz).
3c. 1H NMR (CD2Cl2, -30 °C): δ 0.98 (d, JPH ) 8.1 Hz,
3
2JPtH ) 22.2 Hz, 6H, PMe), 1.33 (d, 3JPH ) 8.1 Hz, 2JPtH ) 16.2
Hz, 6H, PMe), 3.77 (s, 9H, OMe), 4.92 (dddd, 3JHH ) 19.2 Hz,
2JHH ) 4.5 Hz, JPH ) 8.7 and 4.5 Hz, JPtH ) 73.8 Hz, 1H,
4
3
1
carried out. Complexes 4a-e were identified by H, 31C{1H},
3
2
4
PtCHdCH2), 5.66 (dddd, JHH ) 13.5 Hz, JHH ) 4.5 Hz, JPH
and 31P{1H} NMR spectroscopy.
3
) 17.1 and 4.5 Hz, JPtH ) 132.9 Hz, 1H, PtCHdCH2), 6.82
3
1
2
(d, JHH ) 8.7 Hz, 6H, Ar), 7.01 (m, 1H, PtCHdCH2), 7.15-
4a. H NMR (toluene-d8, 20 °C): δ 1.06 (d, JPH ) 6.9 Hz,
7.5 (m, 10H, Ph), 7.60 (d, 3JHH ) 8.7 Hz, 6H, Ar). 13C{1H} NMR
(CD2Cl2, -30 °C): δ 12.1 (d, 1JPC ) 27 Hz, 2JPtC ) 25 Hz, PMe),
15.9 (dd, 1JPC ) 30 Hz, 3JPC ) 3 Hz, 2JPtC ) 31 Hz, PMe), 54.8
3JPtH ) 30.0 Hz, 3H, PMe), 1.12 (d, 2JPH ) 6.9 Hz, 3JPtH ) 27.6
2
3
Hz, 3H, PMe), 1.28 (d, JPH ) 7.2 Hz, JPtH ) 31.2 Hz, 3H,
PMe), 1.39 (d, 2JPH ) 7.2 Hz, 3JPtH ) 31.8 Hz, 3H, PMe), 2.11
(m, 1H, SiCHdCH2), 2.45 (m, 2H, SiCHdCH2), 6.95-7.35 (m,
19H, Ph), 7.85 (m, 6H, Ph). 13C{1H} NMR (toluene-d8, 20 °C):
3
(s, OMe), 112.2 (s, SiAr), 116.9 (d, JPC ) 9 Hz, PtCHdCH2),
128.1 (d. 3JPC ) 9 Hz, PPh), 128.2 (d, 3JPC ) 9 Hz, PPh), 129.1
2
1
3
2
(s, PPh), 129.5 (s, PPh). 130.6 (d, JPC ) 10 Hz, PPh), 130.8
δ 18.4 (dd, JPC ) 24 Hz, JPC ) 5 Hz, JPtC ) 45 Hz, PMe),
2
3
2
2
1
(d, JPC ) 11 Hz, PPh), 136.0 (dd, JPC ) 6 and 2 Hz, JPtC
)
19.6 (m, PMe), 27.3 (dd, JPC ) 29 and 4 Hz, JPtC ) 216 Hz,
53 Hz, SiAr), 137.6 (d, 1JPC ) 34 Hz, PPh), 138.2 (d, 2JPtC ) 21
2
1
SiCHdCH2), 35.2 (dd, JPC ) 32 and 4 Hz, JPtC ) 211 Hz,
1
3
SiCHdCH2), 127.6 (s, SiPh), 128.0 (d, 3JPC ) 9 Hz, PPh), 128.2
Hz, SiAr), 139.5 (dd, JPC ) 43 Hz, JPC ) 5 Hz, PPh), 158.7
2
1
3
2
(s, SiAr), 159.5 (dd, JPC ) 94 and 16 Hz, JPtC ) 684 Hz,
(d, JPC ) 9 Hz, PPh), 128.6 (s, SiPh), 128.7 (d, JPC ) 2 Hz,
PPh), 128.8 (d, 2JPC ) 2 Hz, PPh), 130.7 (d, 2JPC ) 12 Hz, 3JPtC
PtCHdCH2). 31P{1H} NMR (CD2Cl2, -30 °C): δ -13.5 (d, 2JPP
) 21 Hz, 1JPtP ) 1994 Hz), -5.2 (d, 2JPP ) 21 Hz, 1JPtP ) 1290
2
3
) 21 Hz, PPh), 130.8 (d, JPC ) 12 Hz, JPtC ) 20 Hz, PPh),
Hz). 195Pt{1H} NMR (CD2Cl2, -30 °C): δ -4757 (dd, JPPt
)
1
4
3
136.9 (s, SiPh), 139.3 (d, JPC ) 3 Hz, JPtC ) 14 Hz, SiPh),
1
1
3
1
2006 and 1299 Hz, JPtSi ) 1378 Hz).
141.9 (dd, JPC ) 34 Hz, JPC ) 4 Hz, PPh), 142.5 (dd, JPC
)
35 Hz, 3JPC ) 4 Hz, PPh). 31P{1H} NMR (toluene-d8, 20 °C): δ
-7.6 (d, 2JPP ) 49 Hz, 1JPtP ) 3581 Hz), -6.7 (d, 2JPP ) 49 Hz,
1JPtP ) 3538 Hz).
1
3
3d. H NMR (CD2Cl2, -30 °C): δ 0.51 (s, JPtH ) 26.4 Hz,
3H, SiMe), 1.07 (d, 2JPtH ) 8.1 Hz, 3JPtH ) 23.4 Hz, 6H, PMe),
1.38 (d, 2JPtH ) 8.1 Hz, 3JPtH ) 16.8 Hz, 6H, PMe), 4.97 (dddd,
3JHH ) 19.5 Hz, 2JHH ) 4.4 Hz, 4JPH ) 8.4 and 4.4 Hz, 3JPtH
74.4 Hz, 1H, PtCHdCH2), 5.88 (dddd, 3JHH ) 13.2 Hz, 2JHH
)
)
4b. H NMR (toluene-d8, 20 °C): δ 1.11 (d, JPH ) 6.9 Hz,
1
2
3JPtH ) 30.0 Hz, 3H, PMe), 1.17 (d, 2JPH ) 6.6 Hz, 3JPtH ) 28.2
4.4 Hz, 4JPH ) 18.0 and 4.4 Hz, 3JPtH ) 147.1 Hz, 1H, PtCHd
CH2), 7.1-7.7 (m, 26 H, Ph and PtCHdCH2). 13C{1H} NMR
(CD2Cl2, -30 °C): δ 2.3 (dd, 3JPC ) 4 and 2 Hz, 2JPtC ) 64 Hz,
Hz, 3H, PMe), 1.30 (d, JPH ) 7.2 Hz, JPtH ) 30.6 Hz, 3H,
PMe), 1.39 (d, 2JPH ) 6.9 Hz, 3JPtH ) 31.8 Hz, 3H, PMe), 2.16
(m, 1H, SiCHdCH2), 2.18 (s, 9H, Me), 2.50 (m, 2H, SiCHd
CH2), 6.95-7.15 (m, 12H, Ph and Ar), 7.22-7.38 (m, 4H, Ph),
2
3
1
3
2
SiMe), 12.6 (dd, JPC ) 26 Hz, JPC ) 3 Hz, JPtC ) 24 Hz,
PMe), 16.5 (dd, 1JPC ) 30 Hz, 3JPC ) 5 Hz, 2JPtC ) 35 Hz, PMe),
7.82 (d, JHH ) 7.8 Hz, 6H, Ar). 13C{1H} NMR (toluene-d8, 20
3
3
1
3
2
118.1 (d, JPC ) 8 Hz, PtCHdCH2), 126.7 (s, SiPh), 126.9 (s.
°C): δ 18.6 (dd, JPC ) 24 Hz, JPC ) 5 Hz, JPtC ) 44 Hz,
SiPh), 128.1 (d, 3JPC ) 9 Hz, PPh), 128.2 (d, 3JPC ) 9 Hz, PPh),
PMe), 19.7 (m, PMe), 21.5 (s, Me), 28.2 (dd, JPC ) 29 and 4
2
2
129.2 (s, PPh), 129.4 (s, PPh), 130.6 (d, JPC ) 11 Hz, PPh),
Hz, 1JPtC ) 213 Hz, SiCHdCH2), 35.4 (dd, 2JPC ) 32 and 5 Hz,
1JPtC ) 208 Hz, SiCHdCH2), 127.9 (d, 3JPC ) 9 Hz, PPh), 128.1
130.7 (d, 2JPC ) 12 Hz, PPh), 135.7 (d, 4JPC ) 1 Hz, 2JPtC ) 20
1
3
3
2
Hz, SiPh), 137.9 (dd, JPC ) 34 Hz, JPC ) 2 Hz, PPh), 139.4
(d, JPC ) 9 Hz, PPh), 128.4 (s, SiAr), 128.6 (d, JPC ) 2 Hz,
1
3
3
(dd, JPC ) 44 Hz, JPC ) 7 Hz, PPh), 147.8 (dd, JPC ) 7 and
PPh), 128.8 (d, 2JPC ) 2 Hz, PPh), 130.8 (d, 2JPC ) 12 Hz, 3JPtC
2
2
2
3
3 Hz, JPtC ) 49 Hz, SiPh), 159.0 (dd, JPC ) 96 and 15 Hz,
) 21 Hz, PPh), 130.8 (d, JPC ) 12 Hz, JPtC ) 20 Hz, PPh),
136.2 (d, JPC ) 3 Hz, JPtC ) 14 Hz, SiAr), 137.0 (s, SiAr),
1JPtC ) 683 Hz, PtCHdCH2). 31P{1H} NMR (CD2Cl2, -30 °C):
4
3

cis-Vinyl(silyl)platinum(II) Complexes
Organometallics, Vol. 24, No. 10, 2005 2515
1
3
2
1
137.8 (s, SiAr), 142.0 (dd, JPC ) 34 Hz, JPC ) 4 Hz, PPh),
206 Hz, SiCHdCH2), 35.2 (dd, JPC ) 33 and 5 Hz, JPtC )
1
3
142.8 (dd, JPC ) 35 Hz, JPC ) 3 Hz, PPh). 31P{1H} NMR
208 Hz, SiCHdCH2), 127.5 (s, SiPh), 127.7 (s, SiPh), 128.1 (s,
(toluene-d8, 20 °C): δ -7.6 (d, 2JPP ) 51 Hz, 1JPtP ) 3577 Hz),
PPh), 128.2 (s, PPh), 128.8 (s, SiPh), 129.5 (s, SiPh), 130.7 (d,
2
1
3
2
-6.6 (d, JPP ) 51 Hz, JPtP ) 3544 Hz).
2JPC ) 12 Hz, JPtC ) 22 Hz, PPh), 131.0 (d, JPC ) 13 Hz,
1
2
4c. H NMR (toluene-d8, 20 °C): δ 1.13 (d, JPH ) 7.2 Hz,
3JPtC ) 21 Hz, PPh), 135.2 (s, SiPh), 135.6 (s, SiPh), 135.6 (s,
3JPtH ) 30.0 Hz, 3H, PMe), 1.18 (d, 2JPH ) 6.9 Hz, 3JPtH ) 27.6
3JPtC ) 14 Hz, SiPh), 141.5 (dd, JPC ) 32 Hz, JPC ) 3 Hz,
PPh), 142.3 (dd, 1JPC ) 24 Hz, 3JPC ) 3 Hz, PPh). 31P{1H} NMR
(toluene-d8, 20 °C): δ -7.5 (d, 2JPP ) 51 Hz, 1JPtP ) 3573 Hz),
1
3
2
3
Hz, 3H, PMe), 1.30 (d, JPH ) 7.5 Hz, JPtH ) 30.6 Hz, 3H,
PMe), 1.43 (d, 2JPH ) 7.5 Hz, 3JPtH ) 31.2 Hz, 3H, PMe), 2.21
(m, 1H, SiCHdCH2), 2.51 (m, 2H, SiCHdCH2), 3.38 (s, 9H,
OMe), 6.80 (d, 3JHH ) 8.4 Hz, 6H, Ar), 6.98-7.14 (m, 6H, Ph),
2
1
-6.2 (d, JPP ) 51 Hz, JPtP ) 3544 Hz).
1
2
4e. H NMR (toluene-d8, 20 °C): δ 1.23 (d, JPH ) 7.2 Hz,
7.24-7.38 (m, 4H, Ph), 7.81 (d, JHH ) 8.4 Hz, 6H, Ar). 13C-
3JPtH ) 31.8 Hz, 3H, PMe), 1.33 (d, 2JPH ) 6.9 Hz, 3JPtH ) 32.4
3
{1H} NMR (toluene-d8, 20 °C): δ 18.5 (dd, JPC ) 24 Hz, JPC
Hz, 3H, PMe), 1.50 (d, JPH ) 6.6 Hz, JPtH ) 29.2 Hz, 6H,
PMe), 2.1-2.5 (m, 3H, SiCHdCH2), 6.95-7.36 (m, 12H, Ph),
7.4-7.6 (m, 4H, Ph), 7.54-7.86 (m, 4H, Ph). 13C{1H} NMR
(toluene-d8, 20 °C): δ 18.0-19.8 (m, PMe), 27.3 (dd, 2JPC ) 22
1
3
2
3
2
2
) 4 Hz, JPtC ) 44 Hz, PMe), 19.8 (m, PMe), 28.7 (dd, JPC
)
30 and 5 Hz, 1JPtC ) 214 Hz, SiCHdCH2), 35.4 (dd, 2JPC ) 33
1
and 5 Hz, JPtC ) 210 Hz, SiCHdCH2), 54.4 (s, OMe), 113.4
3
3
2
1
2
(s, SiAr), 128.0 (d, JPC ) 9 Hz, PPh), 128.2 (d, JPC ) 9 Hz,
Hz, JFC ) 19 Hz, JPtC ) 176 Hz, SiCHdCH2), 34.5 (dd, JPC
PPh), 128.7 (d, 2JPC ) 2 Hz, PPh), 128.8 (d, 2JPC ) 2 Hz, PPh),
) 28 and 3 Hz, JPtC ) 227 Hz, SiCHdCH2), 127.4 (s, SiPh),
1
2
3
2
130.7 (d, JPC ) 12 Hz, JPtC ) 21 Hz, PPh), 130.9 (d, JPC
)
127.9 (s, SiPh), 128.0 (s, PPh), 128.1 (s, PPh), 128.8 (s, PPh),
13 Hz, 3JPtC ) 21 Hz, PPh), 130.8 (d, 4JPC ) 3 Hz, SiAr), 138.3
128.9 (s, PPh), 129.4 (s, SiPh), 129.6 (s, SiPh), 130.7 (s, JPtC
3
1
3
(s, SiAr), 142.0 (dd, JPC ) 35 Hz, JPC ) 2 Hz, PPh), 142.7
) 21 Hz, PPh), 130.8 (s, 3JPtC ) 21 Hz, PPh), 135.5 (d, 3JFC
)
(dd, JPC ) 36 Hz, JPC ) 3 Hz, PPh), 160.6 (s, SiAr). 31P{1H}
2 Hz, SiPh), 135.8 (d, JFC ) 1 Hz, SiPh), 136.7 (d, JFC ) 19
1
3
3
2
NMR (toluene-d8, 20 °C): δ -7.7 (d, 2JPP ) 51 Hz, 1JPtP ) 3568
Hz, SiPh), 141.4 (d, JPC ) 40 Hz, PPh), 142.4 (d, JPC ) 38
1
1
2
1
Hz), -6.4 (d, JPP ) 51 Hz, JPtP ) 3544 Hz).
Hz, PPh). 31P{1H} NMR (toluene-d8, 20 °C): δ -7.7 (d, 2JPP
)
4d. 1H NMR (toluene-d8, 20 °C): δ 0.55 (s, 3H, SiMe), 1.19
47 Hz, JFP ) 16 Hz, JPtP ) 3734 Hz), -7.1 (d, JPP ) 47 Hz,
4
1
2
2
3
2
(d, JPH ) 7.2 Hz, JPtH ) 30.0 Hz, 3H, PMe), 1.21 (d, JPH
)
1JPtP ) 3450 Hz).
6.9 Hz, 3JPtH ) 32.4 Hz, 3H, PMe), 1.30 (d, 2JPH ) 7.5 Hz, 3JPtH
) 30.6 Hz, 3H, PMe), 1.40 (d, JPH ) 7.5 Hz, 3JPtH ) 31.8 Hz,
2
Acknowledgment. This work was supported by a
Grant-in-Aid for Scientific Research from the Ministry
of Education, Culture, Sports, Science and Technology
of Japan (Nos. 14078222 and 15350060).
3H, PMe), 2.1-2.5 (m, 3H, SiCHdCH2), 6.95-7.36 (m, 12H,
Ph), 7.4-7.6 (m, 4H, Ph), 7.54-7.86 (m, 4H, Ph). 13C{1H} NMR
4
3
(toluene-d8, 20 °C): δ -0.96 (d, JPC ) 2 Hz, JPtC ) 22 Hz,
1
3
2
SiMe), 18.5 (dd, JPC ) 25 Hz, JPC ) 4 Hz, JPtC ) 44 Hz,
2
1
PMe), 19.6 (m, PMe), 29.7 (dd, JPC ) 29 and 5 Hz, JPtC
)
OM0580001