Synthesis and crystal structures of platinum (II) complexes with phosphine sulfide: cis-Dichloro[dimethylsulfoxide](triphenylphosphine sulfide) platinum (II) and (−)-cis-dichloro[(S)-methyl-p-tolylsulfoxide](triphenylphosphine sulfide) platinum (II

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• 作者：Alexej N. Skvortsov ; Alexander N. Reznikov ; Dimitry A. de Vekki ; Adam I. Stash ; Vitaly K. Belsky ; Vitaly N. Spevak and Nickolaj K. Skvortsov
• 关键词：Phosphine sulfide ; Triphenylphosphine sulfide ; Sulfoxide ; Platinum complexes ; Optical activity ; Hydrosilylation
• 刊名：Inorganica Chimica Acta
• 出版年：2006
• 期刊代码：40_00201693
• 类别：ch
• 出版时间：1 March 2006
• 卷：359
• 期：4
• 页码：1031-1040
• 文件大小：232 K

摘要

The addition of triphenylphosphine sulfide (Ph₃PS) to bis-sulfoxide platinum (II) complexes [Pt(Me₂SO)₂Cl₂] and (−)-[Pt(Me-p-TolSO)₂Cl₂] yields mixed ligand complexes [Pt(Ph₃PS)(Me₂SO)Cl₂] (1) and (−)-[Pt(Ph₃PS)(Me-p-TolSO)Cl₂] (2), which are effective catalysts for hydrosilylation reaction. These mixed-ligand complexes were obtained in crystal state and analyzed by X-ray diffraction, ¹H, ³¹P and ¹⁹⁵Pt NMR; 2 was also studied by circular dichroism spectroscopy. Both complexes exist in CDCl₃ 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–Ph₃PS coordination bond, unaffected by chelation or bridging, were evaluated. The lengths of this bond are 2.300(4) in 1 and 2.305(3) 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 Ph₃PS is estimated to be strong and close to that of S-coordinated Me₂SO. 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 Ph₃PS.