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 OPr^i–, 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 OPr^i– 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.