Thermal decomposition of some acyl(dialkyl)-, dialkyl(allyl)-, dialkyl(benzyl)-, and trialkyl-halogenobis(dimethylphenylphosphine)platinum(IV) complexes
Abstract
The complexes [PtR2(R′)X(PMe2Ph)2](X = halogen : R = Me, R′= benzyl or allyl; R = CD3, R′= acetyl; R = Et, R′= Me) have been prepared. On pyrolysis, the benzyl and acetyl complexes undergo reductive elimination with C–C bond formation, the former giving ethane and ethylbenzene and the latter giving CD3COMe as the organic products. Acetone elimination from the complex [PtMe2(COMe)Cl(PMe2Ph)2] has been studied by differential-scanning calorimetry and a mean value of the Pt–C σ-bond energy has been estimated. The complex [PtBr(Me)2(CH2CHCH2)(PMe2Ph)2] apparently decomposes by a free-radical mechanism, and [PtI(Me)Et2(PMe2Ph)2] decomposes by a mechanism involving β-elimination of ethylene as the first step. The relative ease of elimination of a series of alkyl, acyl, and allyl groups from PtIV complexes has been deduced.