197293-60-0Relevant academic research and scientific papers
Syntheses and structural characteristics of [2-thiaalkyl]platinum complexes with phosphorus- and nitrogen-donor ligands
Griffiths, David C.,MacTavish, D. Iain,Male, Nigel A. H.,Tocher, Derek A.,Young, G. Brent
, p. 3373 - 3385 (2007/10/03)
The preparation of a series of bis(2-thiaalkyl)platinum(II) complexes, cis-Pt(CH2SR)2L12 {R = Ph, L1 = PPh3, PMe3, PMe2Ph, PMePh2 or L12 = dppe [1,2-bis(diphenylphosphino)ethane], dmpe [1,2-bis(dimethylphosphino)-ethane], dcpe [1,2-bis(dicyclohexylphosphino)ethane], dppm [bis(diphenylphosphino)methane]; R = C6H4Me-p, L1 = PPh3, PMe3, PMe2Ph or L12 = dppe, dmpe; R = Me, L1 = PPh3, PMe3, PMePh2 or L12 =dppe} and their characterisation by 1H, 13C and 31P NMR spectroscopy, are described. The relative trans influence of a range of heteromethyl ligands, CH2YRn, is discussed [Y = S, Si, Ge, Sn and C; R = (variously) alkyl, aryl, alkenyl or alkynyl; n = (appropriately) 1 or 3]. Also reported are the formation and characteristics of the dinuclear platinum(II) species, [Pt(CH2SCH3)(μ-CH2SCH3)(PPh 3)]2, containing bridging thiaalky] ligands in a six-membered dimetallacycle. Thermolytic rearrangement of Pt(CH2SPh)2(dppe) leads to a metallacyclic product, Pt(C6H4SCH2)(dPPe). The syntheses and spectroscopic identification of asymmetric complexes cis-Pt(CH2SR)R′-(PPh3)2 (R = Ph, R′ = Me, C6H4But-p, CH2CMe2Ph, CH2SiMe2Ph; R = Me, R′ = CH2SiMe3) are also reported, as are unsuccessful attempts to isolate related complexes cis-Pt(CH2SR)2L2 [L2 = polypyridyl N donor; L = P(OMe)3]. The molecular structures of cis-Pt(CH2SPh)2(PPh3) 2·0.5CH2Cl2, [Pt(CH2SCH3)(μ-CH2SCH3)(PPh 3)]2 and cis-Pt(CH2SPh)(CH3)(PPh3)2 have been determined by X-ray diffractometry. Oxidative addition of ClCH2SPh to appropriate dimethylplatinum(II) precursors has afforded two platinum(IV) derivatives, PtCl(CH2SPh)Me2(dmpe) and PtCl(CH2SPh)Me2(bipy) (bipy = 2,2′-bipyridyl), of differing stereochemistry. ? This paper is respectfully dedicated to the memory of Professor Sir Geoffrey Wilkinson, FRS (1921-1996), an inspiring colleague and friend. Geoff was among the first to recognise the significance of heteromethyl ligands, CH2YRn, such as those featured here, and his own work in the area gave great impetus to the development of alkyltransition-metal chemistry.
