reflections measured, 8619 unique, R(I > 2.0s (I)) = 0.059, and Rw(all
reflections) = 0.172. It is possible that methyl H atoms of two C6H4Me-p
groups are incorrectly oriented.
8 (or 10) was reductively eliminated with the regeneration of the
Pd(0)-complex.
In conclusion, this paper revealed that the lone pair of the
heteroatom located at the b-cis position in a,b-unsaturated acyl
and aroyl group 10 metal complexes can significantly promote the
decarbonylation process. Although the coordination of sulfur to
metal has often been considered to suppress catalytic reactions,16
the results described herein clearly substantiate that the sulfur
functionality present at pertinent positions can rather effectively
function as a powerful promoter.
8 It has been reported that stable metalacycles with similar fragments such
as CpM[(Z)-C(O)C(E)LC(E)(SR)](CO)n (M = Fe, Mo, W; E = CF3,
C(O)OMe) have been formed by cycloaddition reactions, see: (a)
M. M. Kubicki, R. Kergoat, H. Scordia, L. C. Gomes de Lima,
J. E. Guerchais and P. L’Haridon, J. Organomet. Chem., 1988, 340, 41;
(b) M. M. Kubicki, L. C. Gomes de Lima, H. Scordia, J. E. Guerchais
and P. L’Haridon, J. Organomet. Chem., 1989, 367, 143; (c) L. Carlton,
J. L. Davidson and M. Shiralian, J. Chem. Soc., Dalton Trans., 1986,
1577; (d) P. Veya, C. Floriani, A. Chiesi-Villa and C. Rizolli,
Organometallics, 1993, 12, 4646; (e) S. Lee, K. Cheung and W. Wong,
J. Organomet. Chem., 1995, 494, 273 and references therein.
9 It has been reported the JPt-P values of trans CO, SAr, and vinyl of
PPh3-ligated Pt(II)-complexes were ranging about >3500 Hz, 2700–
3100 Hz and 1500–1800 Hz, respectively. G. K. Anderson and
R. J. Cross, J. Chem. Soc., Dalton Trans., 1980, 1434. See also ref. 3
and 4.
10 M. Gerisch, F. W. Heinemann, C. Bruhn, J. Scholz and D. Steinborn,
Organometallics, 1999, 18, 564.
11 The 31P NMR spectrum of a solution of 6a and PPh3 (1.5 equiv.)
taken at 270 uC and 250 uC detected mixtures of trans-3a/6a in the
ratios of 56 : 44 and 8 : 92, respectively. See the ESI for more
details.
12 There can be two possible mechanisms. One is the migration of the vinyl
moiety to a vacant coordination site of Pt(II)-complex 6a and the other
is a coplanar slippage of vinyl carbon to the b-cis-SAr coordination site
with the C–S bond gradually cleaved.
Notes and references
1 (a) M. C. Whisler, S. MacNeil, V. Snieckus and P. Beak, Angew. Chem.,
Int. Ed., 2004, 43, 2206; (b) P. Beak, A. Basu, D. J. Gallagher, Y. S. Park
and S. Thayumanavan, Acc. Chem. Res., 1996, 29, 552; (c) V. Snieckus,
Chem. Rev., 1990, 90, 879; (d) P. Beak and A. I. Meyers, Acc. Chem.
Res., 1986, 19, 356; (e) A. H. Hoveyda, D. A. Evans and G. C. Fu,
Chem. Rev., 1993, 93, 1307.
2 For reviews of oxidative addition, see: (a) M. Albrecht and G. van
Koten, Angew. Chem., Int. Ed., 2001, 40, 3750; (b) M. E. van der Boom
and D. Milstein, Chem. Rev., 2003, 103, 1759; (c) V. Ritleng, C. Sirlin
and M. Pfeffer, Chem. Rev., 2002, 102, 1731; (d) F. Kakiuchi and
N. Chatani, Adv. Synth. Catal., 2003, 345, 1077.
3 H. Kuniyasu, T. Kato, Y. Minami, J. Terao and N. Kambe,
Organometallics, submitted.
13 Meyer et al. have recently proposed that a similar coordination by SeAr
to Pd promoted the carbonylation of vinylpalladium. (a) D. J. Knapton
and T. Y. Meyer, J. Org. Chem., 2005, 70, 785; (b) D. J. Knapton and
T. Y. Meyer, Org. Lett., 2004, 6, 687.
14 K. Osakada, T. Yamamoto and A. Yamamoto, Tetrahedron Lett., 1987,
28, 6321.
15 H. Kuniyasu and H. Kurosawa, Chem.–Eur. J., 2002, 8, 2669.
16 L. L. Hegedus and R. W. McCabe, Catalyst Poisoning, Marcel Dekker,
New York, 1984.
4 H. Kuniyasu, A. Ohtaka, M. Kinomoto and H. Kurosawa, J. Am.
Chem. Soc., 2000, 122, 2375.
5 Instead of heating, N2 gas bubbling was also efficient for decarbonyla-
tion to yield 4a selectively in good yield.
6 S. P. Dent, C. Eaborn and A. Pidcock, J. Organomet. Chem., 1975, 97,
307.
7 Crystal data of 6a: space group triclinic P-1 (No. 2) with a = 9.5969(5) A,
˚
˚
˚
b = 11.1578(3) A, c = 19.2187(6) A, a = 83.794(2)u, b = 89.248(5)u, c =
68.512(3)u, Z = 2, r = 1.455 g cm23, m(MoKa) = 38.53 cm21, 18020
870 | Chem. Commun., 2006, 868–870
This journal is ß The Royal Society of Chemistry 2006