Organic reactions involving transition metals. Part V. Nucleophilic attack on co-ordinated dienes by carboxylate ions and a rearrangement reaction of a co-ordinated norbornenyl group

Abstract

The complexes (diene)MCl₂(diene = norbornadiene, dicyclopentadiene, M = Pd, Pt; diene = cyclo-octa-1,5-diene, hexa-1,5-diene, M = Pt) react with silver carboxylates, AgO₂CR (R = CH₃, CH₂Cl, CH₂F, C₆H₅), to give in most cases the complexes [(RCO₂-alkenyl)MO₂CR]₂ in which one double bond of the diene has undergone nucleophilic attack. In three cases the monomeric products (diene)Pt(O₂CR)₂ are obtained (diene = norbornadiene, R = CH₂Cl, CH₂F; diene = cyclo-octa-1,5-diene, R = CH₂F). The n.m.r. spectra of some of the norbornadiene derivatives have been examined and a controversy over band assignments is resolved. The norbornadiene derivatives react with triphenylphosphine to give dimeric products [(RCO₂C₇H₈)M(O₂CR)PPh₃]₂ in which the organic ligand has rearranged to a nortricyclene system.