3
(
0.856 g, 4.64 mmol) and THF (7 cm ) in that order. The mix-
MHz, in CD Cl ) 0.92 (6 H, br s, SiHCH Ph), 1.07 (2 H, br t,
2 2 3
ture was heated at 55 ЊC for 30 min to give a deep red solution.
After the solution was stirred at room temperature for 1 h, the
solvent was evaporated under reduced pressure to give an
orange residue. The addition of hexane and ensuing storage of
the residue for several hours at Ϫ30 ЊC produced an orange
solid which was collected by filtration, washed with hexane, and
recrystallized with THF–hexane to give complex 2 as red crys-
tals (1.18 g, 63%). The filtrate was evaporated under reduced
pressure to give a yellow solid from which 1 was obtained as
pale yellow crystals after recrystallization from ether (0.053 g,
SiH, J(HP) = 2.0 Hz), 7.20, 7.44 (10 H, m, Ph); δ (external 85%
P
H PO standard at 120 MHz in CD Cl ) Ϫ24.3 (s); 6 (30%)
3
4
2
2
(Found: C, 45.37; H, 6.79. C H PPdSi requires C, 45.15; H,
13
24
7.00%); δ (300 MHz, in CD Cl ) 0.80 (18 H, br quintet due to
H
2
2
virtual coupling, PCH CH ), 0.93 (6 H, br s, SiHCH Ph), 0.99
2
3
3
(2 H, br s, SiH), 1.42 (12 H, m, PCH CH ), 7.13, 7.40 (10 H, m,
2
3
31
1
Ph); δ ( P-{ H} from external 85% H PO at 120 MHz in
CD Cl ) 16.7 (s, J( P Si) = 72, 27 Hz).
P
3
4
31
29
2
2
Reaction of Pd(CH ᎐CHPh)L with H SiPh or H SiMePh
2
᎐
2
2
2
2
3
%). Data for 1: mp 105 ЊC (decomp.) (Found: C, 49.08; H,
To a Schlenk flask containing trans-PdEt (PMe ) (0.244 g, 0.77
2
3 2
5
.77. C H PPdSi requires C, 49.25; H, 5.51%); δ (400 MHz,
15
20
H
mmol) at 0 ЊC were added styrene (0.322 g, 3.09 mmol) and
CD Cl at 25 ЊC) 7.63 (8 H, m, C H ), 7.31 (12 H, m, C H ),
2
2
6
5
6
5
3
29
1
THF (3 cm ) in that order. The mixture was heated at 55 ЊC for
1
.77 (2 H, s, SiH, J( Si H) = 77 Hz) and 1.19 (18 H, br, CH );
3
3
h to give a pale yellow solution. The solution was cooled to
(
at 0 ЊC) 7.61 (8 H, m, C H ), 7.33 (4 H, m, C H ), 7.31 (8 H,
6
5
6
29
5
1
31
1
room temperature and H SiPh (0.142 g, 0.77 mmol) added.
2
2
m, C H ), 1.76 (2 H, d, SiH, J( P H) = 7, J( Si H) = 80 Hz)
6
5
The initial red solution instantly turned dark red. After stirring
for 3 h the solvent was removed under reduced pressure to give
a dark red residue. The addition of hexane and ensuing storage
of the product for several hours at Ϫ30 ЊC produced an orange
solid which was collected by filtration and washed with hexane
to give complex 2 (0.257 g, 82%).
and 1.17 (18 H, br, CH ); (at Ϫ30 ЊC) 7.60 (8 H, m, C H ), 7.31
3
6
5
31
1
29
1
(
12 H, m, C H ), 1.72 (2 H, d, SiH, J( P H) = 7, J( Si H) = 77
6 5
Hz) and 1.14 (18 H, br, CH ); (at Ϫ70 ЊC) 7.56 (8 H, m, C H ),
3
6
5
29
1
7
1
.29 (12 H, m, C H ), 1.66 (2 H, br, SiH, J( Si H) = 82 Hz) and
6 5
.10 (18 H, br, CH ); (at Ϫ90 ЊC) 7.53 (8 H, m, C H ), 7.30
3
6
5
29
1
(
(
12 H, m, C H ), 1.62 (2 H, br, SiH, J( Si H) = 80 Hz) and 1.08
18 H, br, CH ); δ (160 MHz in CD Cl ) (at 25 ЊC) Ϫ34.4 (br,
6 5
Reactions of Pd(CH ᎐CHPh)L (L = PMe , PEt or PMePh )
2
2
3
3
2
3
P
2
31
2
29
with equimolar or twofold molar amounts of H
2
SiPh
2
or
ν1/2 = 43 Hz); (at 0 ЊC) Ϫ26.5 (s, J( Si P) = 74 Hz); (at Ϫ30 ЊC)
Ϫ25.8 (s, J( Si P) = 74 and 28 Hz); (at Ϫ70 ЊC) Ϫ25.1 (s,
J( Si P) = 74 Hz); (at Ϫ90 ЊC) Ϫ24.7 (s, J( Si P) = 74 Hz).
Data for 2: mp 109 ЊC (decomp.) (Found: C, 48.75, H, 6.27.
C H P Pd Si requires C, 49.08; H, 6.11%); δ (400 MHz,
29
31
H SiMePh were analogously carried out to give the correspond-
2
29
31
29 31
ing complexes.
Reactions of complex 2
33
49
3
2
2
H
CD Cl ) (at 25 ЊC) 7.63 (8 H, m, C H ), 7.29 (12 H, m, C H ),
3
2
2
6
5
6
5
With alkyne. To an ether (5 cm ) solution of complex 2 (0.106
g, 0.13 mmol) was added diphenylacetylene (0.024 g, 0.13
mmol) at room temperature. The initial red solution slowly
turned dark red. After stirring for 4 h the solvent was removed
under reduced pressure to give a dark red residue. The addition
of hexane and ensuing storage of the product for several hours
at Ϫ30 ЊC enabled the recovery of 2 (0.93 g, 87%). Reaction of
2 with a twofold molar amount of phenylacetylene proceeded
analogously to give the starting material (92%).
29
1
1
.00 (27 H, d, CH , J(PH) = 7) and 0.59 (2 H, br, SiH, J( Si H)
3
=
79 Hz); (at 0 ЊC) 7.63 (8 H, m, C H ), 7.28 (12 H, m, C H ),
6 5 6 5
29 1
0
.93 (27 H, s, CH ) and 0.15 (2 H, br, SiH, J( Si H) = 76 Hz);
3
(
at Ϫ30 ЊC) 7.59 (8 H, m, C H ), 7.29 (12 H, m, C H ), 0.87 (27
6 5 6 5
H, s, CH ) and Ϫ0.17 (2 H, br, SiH, ν = 53 Hz); (at Ϫ70 ЊC)
3
1/2
7
.55 (8 H, br, C H ), 0.99 (10 H, br, CH and SiH), 0.68 (18 H,
6
5
3
br, CH ) and Ϫ2.33 (1 H, br, SiH, ν = 84 Hz); (at Ϫ90 ЊC) 7.53
3
1/2
(
8 H, m, C H ), 7.27 (12 H, m, C H ), 1.24 (1 H, d, SiH,
6 5 6 5
31 1 29 1
J( P H) = 8 Hz, J( Si H) = 84 Hz), 1.03 (9 H, s, CH ), 0.63
(
3
31
1
29
1
18 H, s, CH ), Ϫ2.34 (1 H, t, SiH, J( P H) = 11, J( Si H) = 86
3
With CO. Complex 2 (0.145 g, 0.18 mmol) was dissolved in
Hz); (160 MHz in CD Cl ) (at 25 ЊC) Ϫ34.4 (br, ν = 43 Hz);
3
2
2
1/2
toluene (3 cm ) at room temperature. After evacuation of the
(
1
8
a
t
0
Њ
C
)
Ϫ
3
3
.
3
(
b
r
,
ν
=
4
3
H
z
)
;
(
a
t
Ϫ
3
0
Њ
C
)
Ϫ
3
2
.
2
(
b
r
,
ν
=
=
1
/
2
1
/
2
system, CO (1 atm) was introduced and the initial red solution
turned dark red. After stirring for 1 h the solvent was evapor-
ated under reduced pressure to give an oily residue. The addi-
02 Hz); (at Ϫ70 ЊC) Ϫ26.4 (br, ν1 = 98) and Ϫ33.6 (br, ν
/2 1/2
31 31 29 31
1 Hz); (at Ϫ90 ЊC) Ϫ25.9 (t, J( P P) = 23, J( Si P) = 129)
31
31
29 31
and Ϫ33.0 (t, J( P P) = 23, J( Si P) = 42 Hz).
3
tion of hexane (2 cm ) and ensuing storage of the residue for
several hours at Ϫ30 ЊC produced an orange solid which was
collected by filtration and washed with hexane (1 cm × 3) to
give 1 (0.104 g, 79%).
Complexes 3–6. To a Schlenk flask containing trans-
PdEt (PEt ) (0.171 g, 0.43 mmol) at 0 ЊC were added H SiPh
3
2
3
2
2
2
3
(
0.079 g, 0.43 mmol) and THF (3 cm ) in that order. The
mixture was heated at 55 ЊC for 30 min to give a deep orange
solution which was stirred for an additional 1 h at room tem-
perature. The solvent was evaporated under reduced pressure to
give an orange residue. The addition of hexane and ensuing
storage of the product for several hours at Ϫ30 ЊC produced
an orange solid which was collected by filtration, washed with
hexane, and recrystallized from ether–hexane to give complex
3
With HSPh. To an ether (6 cm ) solution of complex 2 (0.125
g, 0.15 mmol) was added benzenethiol (0.034 g, 0.30 mmol) at
room temperature. The initial red solution slowly turned orange
accompanied by gradual formation of the solid product. After
stirring for 1 h the reaction mixture was stored at Ϫ30 ЊC for
several hours to cause complete precipitation of a yellow solid
which was collected by filtration, washed with hexane (2 cm ×
) and dried in vacuo to give 7 (0.032 g, 43%). δ (300 MHz, in
CD Cl ) 1.31 (18 H, s, P(CH ) , J(PH) = 3.4 Hz), 6.80 (1 H, t,
Ph), 7.19 (2 H, t, Ph) and 7.68 (2 H, d, Ph). δ ( P-{ H} from
external 85% H PO at 120 MHz in CD Cl ) Ϫ13.1 (s). Complex
was also obtained from the reaction of trans-PdMe (PMe )
3
3
6
as pale yellow crystals (0.105 g, 60%) (Found: C, 52.70; H,
2
H
.74. C H PPdSi requires C, 53.01; H, 6.43%); δ (300 MHz,
18
26
H
2
2
3 3
in CD Cl ) 0.85 (18 H, br quintet due to virtual coupling,
31
1
2
2
P
PCH CH ), 1.50 (12 H, m, PCH CH ), 1.76 (2 H, br d, Si–H,
2
3
2
3
1
29
3
4
2
2
J( H Si) = 78), J(HP) = 4.8 Hz), 7.32, 7.67 (20 H, m, Ph);
δ ( P-{ H} from external 85% H PO at 120 MHz in CD Cl )
5.3 (s, J( P Si) = 69, 27 Hz).
Complexes 4–6 were prepared analogously: 4 (52%) (Found:
C, 61.61; H, 5.02. C H PPdSi requires C, 61.29; H, 4.94);
7
3
1
1
2 3 2
P
3
4
2
2
with an excess of benzenethiol and identified using the spectro-
3
1
29
1
scopic data.
25
24
Crystallography
δ (300 MHz, in CD Cl ) 1.67 (6 H, s, PCH Ph ), 2.15 (2 H, br s,
H
2
2
3
2
31
1
SiH) and 7.17–7.49 (40 H, m, Ph); δ ( P{- H} from external
Crystals of complexes 3 and 5 suitable for X-ray diffraction
study were obtained by recrystallization from ether–hexane and
mounted in glass capillary tubes under argon. Intensities were
collected for Lorentz-polarization effects on a Rigaku AFC-5R
P
31
29
8
5% H PO at 120 MHz in CD Cl ) 7.89 (s); (J( P Si) not
3 4 2 2
obtained due to broading of signal; 5 (39%) (Found: C, 39.27;
H, 5.66. C H PPdSi requires C, 39.54; H, 5.97%); δ (300
10
18
H
4
20
J. Chem. Soc., Dalton Trans., 2000, 417–421