Reactions involving transition metals. Part XI. Reactions of nucleophiles with dieneplatinum complexes

Abstract

The reactions of the complexes [Pt(diene)Cl2](diene = norbornadiene or dicyclopentadiene) with the nucleophiles OPri–, NH2Ph, SPh–, and SCN– have been investigated. The dicyclopentadiene complex undergoes attack at the diene in each case and the S-nucleophiles also give substitution at platinum. Onlythelatterreactionoccurswith the norbornadiene complexes and S-nucleophiles, but attack on the organic ligand is found with OPri– and NH2Ph, The reactions of these products with neutral uni- and bi-dentate ligands usually leads to bridge-splitting reactions, but in some cases the norbornenyl derivatives undergo rearrangement to nortricyclene systems. The reaction of the alkenyl complexes with a further nucleophile (OMe– or NHPh–) to give doubly σ-bonded alkyleneplatinum complexes is described.