Reactivity of platinum diolefin complexes. 2. Reactions with bulky and chelating group 5B ligands and studies relating to carbonyl insertion

Article abstract of DOI:10.1021/ic50225a005

Reactions of [PtXY(cod)] (X = Y = Cl, Me, Ph; X = Cl, Y = Ph, COPh) with bulky monodentate and chelating group 5B ligands have been examined by ³¹P{¹H} NMR spectroscopy. The molecularity of the products is a function of steric bulk with monodentate ligands and a function of chelate bite with bidentate ligands. The geometry of the products is controlled largely by the trans influence of both neutral and anionic groups. Where the steric constraints involved in nucleophilic attack of the complexes by bulky ligands are dominant, olefin displacement can be prevented entirely. Reactions of [PtXYL₂] (X = Y = Ph, Cl; X = Ph, Y = Cl; L = monodentate ligand, L₂ = bidentate ligand) with carbon monoxide have been studied by ³¹P{¹H} and ¹³C{¹H} NMR and infrared spectroscopies. The mechanism of carbonyl insertion at platinum(II) is discussed in terms of the chelate effect and the trans influence of the anionic ligands.