Issue 5, 1994

Highly stereospecific carbene insertions into platinum–halide bonds. Crystal structure of [PtCl(S-CHClSiMe3)(S,S-Ph2PCHMeCH2CHMePPh2)]

Abstract

Trimethylsilyldiazomethane reacted with [PtX2L2][X = Cl, Br or I; L2= cycloocta-1,5-diene (cod) or Ph2P(CH2)nPPh2 where n= 1–4] to give the corresponding [PtX(CHXSiMe3)L2] as a racemic mixture in high yields. The cod ligands in [PtX(CHXSiMe3)(cod)] were readily displaced by diphosphines. When optically active complexes [PtX2L2][X = Cl, Br or I; L2=(2S,3S)-2,3-bis(diphenylphosphino)butane, (2S,4S)-2,4-bis(diphenylphosphino)pentane (S,S-skewphos) or (4R,5R)-4,5-bis(diphenylphosphinomethyl )-2,2-dimethyl-1,3-dioxolane] were treated with trimethylsilyldiazomethane the products [PtX(CHXSiMe3)L2] were mixtures of diastereoisomers in different proportions ranging from 1 : 1 to 15 : 1. The major diastereoisomer of [PtCl(CHClSiMe3)(S,S-skewphos)] was readily separated by fractional crystallisation and its crystal structure revealed that the configuration at the α-carbon was S. This compound is configurationally stable for at least 14 d in CDCl3 solution as shown by 31P NMR spectroscopy. The high diastereoselectivities obtained in some of the reactions may originate from steric effects.

Article information

Article type
Paper

J. Chem. Soc., Dalton Trans., 1994, 651-655

Highly stereospecific carbene insertions into platinum–halide bonds. Crystal structure of [PtCl(S-CHClSiMe3)(S,S-Ph2PCHMeCH2CHMePPh2)]

P. Bergamini, E. Costa, A. G. Orpen, C. Ganter and P. G. Pringle, J. Chem. Soc., Dalton Trans., 1994, 651 DOI: 10.1039/DT9940000651

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