Synthesis of spy-5
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1011; (c) J. Y. Corey, Chem. Rev., 2011, 111, 863–1071.
3 For examples of reaction of Ni complexes with Si–H to give H–Ni–Si
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R. A. Fischer, Angew. Chem., Int. Ed., 2004, 43, 2299–2302; (b) V. M.
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To a solution of Pt(PPh3)4 (37.3 mg, 0.030 mmol) in THF-d8
(0.5 mL) was added 1 (17.0 mg, 0.030 mmol) at -60 ◦C, and
then the mixture was warmed to -20 ◦C. Complex spy-4 was
observed as a sole product by 1H, 31P and 29Si NMR spectroscopy
and was confirmed to be stable at -20 ◦C overnight. Characteristic
resonances of spy-5: 1H NMR (THF-d8, 500 MHz, 253 K) d -7.88
4 Examples for Pd complexes: (a) R. C. Boyle, J. T. Mague and M. J. Fink,
J. Am. Chem. Soc., 2003, 125, 3228–3229; (b) R. C. Boyle, D. Pool, H.
Jacobsen and M. J. Fink, J. Am. Chem. Soc., 2006, 128, 9054–9055.
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H–Pt–Si complexes, see: (a) C. Eaborn, A. Pidcock and B. Ratcliff,
J. Organomet. Chem., 1972, 43, C5–C6; (b) C. Eaborn, B. Ratcliff and
A. Pidcock, J. Organomet. Chem., 1974, 65, 181–186; (c) H. Azizian,
K. R. Dixon, C. Eaborn, A. Pidcock, N. M. Shuaib and J. Vinaixa,
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1
(1H, td, J = 62.7, 16.6 Hz, J(H, Pt) = 1230 Hz), 1.20 (3H, s),
6.12–6.18 (4H, m), 6.86 (6H, t, J = 7.2 Hz), 6.92–7.05 (16H, m),
7.05–7.14 (8H, m), 7.50–7.58 (2H, m), 7.68–7.74 (3H, m), 7.93
1
(2H, d, J = 7.3 Hz); 31P{ H} NMR (THF-d8, 202 MHz, 253 K) d
15.6 (t, J = 14.2 Hz, 1J(P,Pt) = 2174 Hz, 1P), 24.4 (d, J = 14.2 Hz,
1J(P,Pt) = 2519 Hz, 2P); 29Si NMR (THF-d8, 100 MHz, 253 K) d
32.7 (dt, J = 135, 7.2 Hz, 1J(Si,Pt) = 680 Hz, 1J(Si,H) was estimated
to be less than 20 Hz by non1H-decoupled 29Si NMR).
General procedure for the kinetic experiments (Table 4)
To a solution of Pt(PPh3)4 (37.3 mg, 0.030 mmol) in THF-d8
(0.5 mL) was added 1 (17.0 mg, 0.030 mmol) at -60 ◦C, and
then the mixture was warmed to -20 ◦C. After the formation
1
of spy-4 was confirmed by H and 31P NMR spectroscopy, the
NMR sample was warmed to 303 K and the decay of spy-4 and
the formation of tbp-5 was monitored by 31P NMR spectroscopy
(entry 1). Other experiments in entries 2–5 were carried out
according to this procedure under corresponding conditions.
6 W. Chen, S. Shimada, M. Tanaka, Y. Kobayashi and K. Saigo, J. Am.
Chem. Soc., 2004, 126, 8072–8073.
7 S. J. Mitton, R. McDonald and L. Turculet, Organometallics, 2009, 28,
5122–5136.
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Trans., 1980, 659–666; (b) Y.-J. Kim, S.-C. Lee, J.-I. Park, K. Osakada,
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1999, 18, 2583–2586; (d) J. Braddock-Wilking, Y. Levchinsky and
N. P. Rath, Organometallics, 2000, 19, 5500–5510; (e) Y.-J. Kim, S.-
C. Lee, J.-I. Park, K. Osakada, J.-C. Choi and T. Yamamoto, J. Chem.
Soc., Dalton Trans., 2000, 417–421; (f) L. M. Sanow, M. Chai, D. B.
McConnville, K. J. Galat, R. S. Simons, P. L. Rinaldi, W. J. Youngs
and C. A. Tessier, Organometallics, 2000, 19, 192–205; (g) M. Tanabe,
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Osakada, Organometallics, 2005, 24, 4029–4038; (i) M. Tanabe, D. Ito
and K. Osakada, Organometallics, 2008, 27, 2258–2267, and references
cited therein.
9 (a) M. C. MacInnis, D. F. MacLean, R. J. Lundgren, R. McDonald and
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6636–6638.
10 Utilization of a tris(phosphino)silyl ligand with the phenylene back-
bone has been studied by Peters et al. For selected examples, see: (a) N. P.
Mankad, M. T. Whited and J. C. Peters, Angew. Chem., Int. Ed., 2007,
46, 5768–5771; (b) M. T. Whited, N. P. Mankad, Y. Lee, P. F. Oblad and
J. C. Peters, Inorg. Chem., 2009, 48, 2507–2517; (c) Y. Lee, N. P. Mankad
and J. C. Peters, Nat. Chem., 2010, 2, 558–565; (d) N. P. Mankad, P.
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11 See also: (a) S. Kuramochi, Y. Kido, S. Shioda, M. Minato, M.
Kakeya and K. Osakada, Bull. Chem. Soc. Jpn., 2010, 83, 165–169,
and references cited therein; (b) P. Gualco, T.-P. Lin, M. Sircoglou, M.
Mercy, S. Ladeira, G. Bouhadir, L. M. Pe´rez, A. Amgoune, L. Maron,
F. P. Gabbaˆı and D. Bourissou, Angew. Chem., Int. Ed., 2009, 48,
Crystal structure determination
Single crystals were obtained by slow diffusion of pentane into
a solution of the complexes in THF for 2 and 4 and by slow
diffusion of Et2O into a solution of the complex in THF for 3.
Diffraction data were collected on Bruker SMART 1000 system
for 2, on Rigaku RAXIS-RAPID system for 3 and on Rigaku
Mercury CCD system for 4 using graphite-monochromated Mo-
˚
Ka radiation (l = 0.7107 A). Structures were solved by direct
methods using SHELX program package. Hydrogen atoms on Si
in 2 and 3 were located in the final electron density map and refined
isotropically. Disorder of one of the Ph ring on P was observed
in 2.
Acknowledgements
This research was supported by a Grant-in-Aid for Scientific
Research on Innovative Areas "Molecular Activation Directed
toward Straightforward Synthesis" (no. 22105006) from the Min-
istry of Education, Culture, Sports, Science, and Technology of
Japan. We thank Prof. Hidehiro Uekusa and Ms. Sachiyo Kubo
for performing X-ray analysis.
Notes and references
1 (a) U. Schubert, Adv. Organomet. Chem., 1990, 30, 151–187; (b) R. H.
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Chem. Soc. Rev., 2002, 31, 239–245; (e) G. Nikonov, Adv. Organomet.
Chem., 2005, 53, 217–309.
2 For examples of oxidative addition of a H–Si bond to group 10 metals
to give silyl metal complexes, see: (a) J. Y. Corey and J. Braddock-
Wilking, Chem. Rev., 1999, 99, 175–292, and references cited therein;
8820 | Dalton Trans., 2011, 40, 8814–8821
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