A. Skvortsov, A. Reznikov, D. A. de Vekki
Mar 1, 2006
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0
Influential Citations
14
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Journal
Inorganica Chimica Acta
Abstract
Abstract The addition of triphenylphosphine sulfide (Ph 3 PS) to bis-sulfoxide platinum (II) complexes [Pt(Me 2 SO) 2 Cl 2 ] and (−)-[Pt(Me- p -TolSO) 2 Cl 2 ] yields mixed ligand complexes [Pt(Ph 3 PS)(Me 2 SO)Cl 2 ] ( 1 ) and (−)-[Pt(Ph 3 PS)(Me- p -TolSO)Cl 2 ] ( 2 ), which are effective catalysts for hydrosilylation reaction. These mixed-ligand complexes were obtained in crystal state and analyzed by X-ray diffraction, 1 H, 31 P and 195 Pt NMR; 2 was also studied by circular dichroism spectroscopy. Both complexes exist in CDCl 3 solution as a dynamic equilibrium of two geometric isomers with an approximate 1:10 ratio, but only cis -isomer is obtained on crystallization. The X-ray structures of the complexes have classical geometry, and phosphine sulfide and sulfoxides are coordinated via sulfur. The new structural data for simple platinum–Ph 3 PS coordination bond, unaffected by chelation or bridging, were evaluated. The lengths of this bond are 2.300(4) A in 1 and 2.305(3) A in 2 , respectively. PtSP angle equals 105.7(2)° in 1 and 104.05(13)° in 2 , the PtSP plane is almost perpendicular to the coordination plane. The static trans -influence of Ph 3 PS is estimated to be strong and close to that of S -coordinated Me 2 SO. The complex 2 exhibits strong circular dichroism at a wavelength below 330 nm, caused both by inherent Me- p -TolSO stereogenic center and induced asymmetry of Ph 3 PS.