3062 Organometallics, Vol. 25, No. 12, 2006
Pizzo et al.
PCH), 1.06-1.15 (m, CH3). 31P{1H} NMR (δ, CDCl3): 39.45 (d,
PC-trans, 1JPt-P ) 2136 Hz). 19F{1H} NMR (δ, CDCl3): -79.53 (s,
1
2
3
3
P
Cl-trans, JPt-P ) 3654 Hz, JP-P ) 16.1 Hz); 39.54 (m, PC-trans,
OTf), -120.80 (t, o-F, JPt-F ) 267.1 Hz, JF-F ) 18.4 Hz),
1JPt-P ) 2194 Hz). 19F{1H} NMR (δ, CDCl3): -120.62, -121.39
3
-161.52 (t, p-F, JF-F ) 19.1 Hz), -164.89 (m, m-F).
3
(m, o-F), -163.77 (t, p-F, JF-F ) 19.9 Hz), -164.91, -165.54
[Pt(C6F5)(H2O)(dfppe)][OTf] (1f). This compound was prepared
using a procedure similar to that described above for complex 1a
starting from [PtCl(C6F5)(dfppe)] (0.31 g, 0.27 mmol) in acetone
(20 mL) and dichloromethane (20 mL). Yield: 0.344 g, 94%. Anal.
Calc for C33H6F28O4P2PtS: C, 30.79; H, 0.47. Found: C, 30.45;
H, 0.56. 1H NMR (δ, CDCl3): 3.26-3.72 (m, PCH2), 2.72 (s, OH2).
31P{1H} NMR (δ, CDCl3): -9.20 (m, PO-trans, 1JPt-P ) 4712 Hz);
(m, m-F).
[Pt(C6F5)(H2O)(dppm)][OTf] (1a). To a solution of [PtCl(C6F5)-
(dppm)] (0.13 g, 0.16 mmol) in wet dichloromethane (20 mL) was
added 0.50 mL of an acetone solution of AgOTf (0.17 mmol). The
suspension was stirred for 3 h, then the solid AgCl was filtered off
and the solution was concentrated. Upon treatment with n-pentane,
a white solid was obtained, filtered off, and dried under vacuum.
Yield: 0.15 g, 98.1%. Anal. Calc for C32H24F8O4P2PtS: C, 42.07;
1
21.24 (m, PC-trans, JPt-P ) 2176 Hz). 19F{1H} NMR (δ, CDCl3):
-121.49 (m, Pt-C6F5, o-F), -128.50, -128.91 (m, P-C6F5, o-F),
-145.53, -146.37 (m, P-C6F5, p-F), -159.42 (m, Pt-C6F5, p-F),
-161.45 (m, P-C6F5, m-F) -164.01 (m, Pt-C6F5, m-F).
1
H, 2.65. Found: C, 41.89; H, 2.89. H NMR (δ, CDCl3): 7.40-
7.82 (m, Ar), 5.35 (m, PCH2), 2.75 (s, OH2). 31P{1H} NMR (δ,
1
2
CDCl3): -49.73 (d, PO-trans, JPt-P ) 3821 Hz, JP-P ) 59.4 Hz);
-37.80 (m, PC-trans, 1JPt-P ) 1872 Hz). 19F{1H} NMR (δ, CDCl3):
-79.3 (s, OTf), -121.49 (t, o-F, 3JPt-F ) 268 Hz), -160.18 (t,
p-F), -164.29 (m, m-F).
[Pt(C6F5)(H2O)(dippe)][OTf] (1g). This compound was pre-
pared using a procedure similar to that described above for complex
1a starting from [PtCl(C6F5)(dippe)] (0.25 g, 0.38 mmol). Yield:
0.243 g, 77%. Anal. Calc for C21H34F8O4P2PtS: C, 31.86; H, 4.33.
[Pt(C6F5)(H2O)(dppe)][BF4] (1b‚BF4). To a solution of [PtCl-
(C6F5)(dppe)] (0.30 g, 0.38 mmol) in wet dichloromethane (20 mL)
was added 0.94 mL of an acetone solution of AgBF4 (0.40 mmol).
The suspension was stirred for an hour, then the solid AgCl was
filtered off and the solution was concentrated. Upon treatment with
n-pentane, a pale yellow solid was obtained, filtered off, and dried
under vacuum. Yield: 0.263 g, 76%. Anal. Calc for C32H26BF9-
OP2Pt: C, 44.41; H, 3.03. Found: C, 44.65; H, 2.75. 1H NMR (δ,
CDCl3): 7.26-7.80 (m, Ar), 2.81 (s, OH2), 2.13-2.62 (m, PCH2).
1
Found: C, 31.45; H, 4.54. H NMR (δ, CDCl3): 2.11-2.59 (m,
CH), 2.72 (s, OH2), 1.65-2.05 (m, PCH2), 1.00-1.45 (m, CH3).
31P{1H} NMR (δ, CD2Cl2): 61.39 (s, PO-trans, 1JPt-P ) 3930 Hz);
78.65 (m, PC-trans, 1JPt-P ) 2456 Hz). 19F{1H} NMR (δ, CD2Cl2):
-79.31 (s, OTf), -119.57 (m, o-F), -160.68 (m, p-F), -164.57
(m, m-F).
[Pt(C6F5)(H2O)((2S),(3S)-Chiraphos)][OTf] (1h). This com-
pound was prepared using a procedure similar to that described
above for complex 1a starting from [PtCl(C6F5)((2S),(3S)-chira-
1
31P{1H} NMR (δ, CDCl3): 32.07 (d, PO-trans, JPt-P ) 4189 Hz,
1
2JP-P ) 6.3 Hz); 46.38 (m, PC-trans, JPt-P ) 2312 Hz). 19F{1H}
1
phos)] (0.152 g, 0.18 mmol). Yield: 0.142 g, 74%. H NMR (δ,
NMR (δ, CDCl3): -120.52 (m, o-F), -153.21 (s, BF4), -159.44
(s, p-F), -163.46 (s, m-F).
CDCl3): 7.15-8.03 (m, Ar), 2.79 (s, OH2), 2.02-2.64 (m, PCH),
1.02-1.13 (m, CH3). 31P{1H} NMR (δ, CDCl3): 32.60 (d, PO-trans
,
[Pt(C6F5)(H2O)(dppe)][OTf] (1b‚OTf). This compound was
prepared using a procedure similar to that described above for
complex 1a starting from [PtCl(C6F5)(dppe)] (0.30 g, 0.38 mmol).
Yield: 0.313 g, 83.1%. Anal. Calc for C33H26F8O4P2PtS: C, 42.73;
1
1JPt-P ) 4272 Hz,2JP-P ) 16.8 Hz); 45.51 (m, PC-trans, JPt-P
)
2222 Hz). 19F{1H} NMR (δ, CDCl3): -79.34 (s, OTf), -120.91,
-121.77 (m, o-F), -161.30 (m, p-F), -164.41, -165.02 (m, m-F).
1
H, 2.83. Found: C, 42.97; H, 2.59. H NMR (δ, CDCl3): 7.36-
Catalytic Studies. These were carried out in a 2 mL vial fitted
with a screw-capped silicone septum to allow sampling. Stirring
was performed by a Teflon-coated bar driven externally by a
magnetic stirrer. Constant temperature (20 °C) was maintained by
water circulation through an external jacket connected with a
thermostat. The concentration of the commercial 35% H2O2 solution
was checked iodometrically prior to use.
7.52 (m, Ar), 2.78 (s, OH2), 2.05-2.66 (m, PCH2). 31P{1H} NMR
(δ, CDCl3): 31.63 (d, PO-trans, 1JPt-P ) 4353 Hz, 2JP-P ) 6.6 Hz);
1
46.33 (m, PC-trans, JPt-P ) 2309 Hz). 19F{1H} NMR (δ, CDCl3):
-79.27 (s, OTf), -120.73 (m, o-F), -160.86 (m, p-F), -164.68
(m, m-F).
[Pt(C6F5)(H2O)(diphoe)][OTf] (1c). This compound was pre-
pared using a procedure similar to that described above for complex
1a starting from [PtCl(C6F5)(diphoe)] (0.13 g, 0.16 mmol) in
dichloromethane (20 mL). Yield: 0.143 g, 95%. Anal. Calc for
C33H24F8O4P2PtS: C, 42.82; H, 2.61. Found: C, 42.44; H, 2.86.
The required amount of catalyst (0.0166 mmol, 2% with respect
to substrate and oxidant) was placed in solid form in the reactor.
To this was added 1 mL of 1,2-dichloroethane, followed by the
proper amount of substrate (0.83 mmol). After thermostating at the
required temperature for a few minutes, a 35% H2O2 solution in
the appropriate amount (0.83 mmol) was injected through the
septum and time was started.
1H NMR (δ, (CDCl3): 7.33-7.85 (m, Ar), 3.47 (m, PCH), 2.75
1
(s, OH2); 31P{1H} NMR (δ, (CDCl3): 59.03 (m, PC-trans, JPt-P
)
2318 Hz); 33.19 (s, PO-trans, 1JPt-P ) 4441 Hz). 19F{1H} NMR (δ,
(CDCl3): -79.25 (s, OTf), -119.57 (m, o-F), -160.68 (m, p-F),
-164.57 (m, m-F).
All reactions were monitored with GLC by direct injection of
samples taken periodically from the reaction mixtures with a
microsyringe; n-decane was used as internal standard. Initial rate
data were determined from conversion versus time plots. Separation
of the products was performed on a 25 m HP-5 capillary column
using a flame ionization detector.
[Pt(C6F5)(H2O)(dppp)][OTf] (1d). This compound was prepared
using a procedure similar to that described above for complex 1a
starting from [PtCl(C6F5)(dppp)] (0.211 g, 0.26 mmol). Yield: 0.223
g, 91%. Anal. Calc for C34H28F8O4P2PtS: C, 43.37; H, 3.00.
1
Found: C, 43.27; H, 3.12. H NMR (δ, CDCl3): 7.18-7.75 (m,
Ar), 2.73 (s, OH2), 2.08-2.87 (m, CH2). 31P{1H} NMR (δ, CDCl3):
1
-9.36 (d, PO-trans, JPt-P ) 4148 Hz,2JP-P ) 26.9 Hz); 0.91 (m,
1
P
C-trans, JPt-P ) 2128 Hz). 19F NMR (δ, CDCl3): -79.76 (OTf),
Acknowledgment. R.A.M. and G.S. thank MIUR, Universita`
di Padova, and Universita` Ca` Foscari di Venezia for financial
support (PRIN 2003). R.A.M. thanks CIRCC (Consorzio
Interuniversitario Reattivita` Chimica e Catalisi) for a fellowship
to E.P. G.S. wishes to thank Johnson-Matthey for the loan of
platinum. L. Sperni is gratefully acknowledged for GC-MS
analysis.
-120.75 (o-F), -161.38 (p-F), -164.79 (m-F).
[Pt(C6F5)(H2O)(dppb)][OTf] (1e). This compound was prepared
using a procedure similar to that described above for complex 1a
starting from [PtCl(C6F5)(dppb)] (0.15 g, 0.18 mmol). Yield: 0.147
g, 79%. Anal. Calc for C35H30F8O4P2PtS: C, 43.99; H, 3.16.
1
Found: C, 43.87; H, 2.88. H NMR (δ, CDCl3): 7.18-7.61 (m,
Ar), 1.58-2.87 (m, CH2 and s, OH2). 31P{1H} NMR (δ, CDCl3):
1
14.76 (d, PO-trans, JPt-P ) 4530 Hz,2JP-P ) 21.6 Hz); 7.34 (m,
OM060194C