Reactivity of κ(P)-Alkenylphosphane Rhodium(III) and Iridium(III) Complexes toward Nucleophilic Reagents

Abstract

The reactivity of the complexes [RhCl2(η5-C5Me5){κ(P)-Ph2P(CH2)2CH=CH2}] (1), [MCl2(η5-C5Me5){κ(P)-R2PCH2CH=CH2}] (M=Rh, R=Ph (3 a), iPr (3 b); M=Ir, R=Ph (4 a), iPr (4 b)) towards various nucleophilic reagents (carbon-donor, nitrogen-donor and phosphorus-donor) in the presence of a halogen abstractor has been studied. The rhodium e iridium complexes undergo metal coordination of the ligand (L=CNR, CO, Py, P(OPh)3) to give the new cationic complexes [MCl(η5-C5Me5)(L){κ(P)-R2P(CH2)nCH=CH2}][BPh4] (M=Rh, Ir; L=CNR, CO, Py, P(OPh)3) (5-19 a,b). However, the reaction with phosphanes follows a different way depending on the metal. While the rhodium complexes 3 a,b give the expected products [RhCl(η5-C5Me5)(L){κ(P)-R2PCH2CH=CH2}][BPh4] (20 a,b, 21 a and 22 a), the iridium complex 4 a suffer addition of the phosphane to the C=C affording the complexes [IrCl(η5-C5Me5){κ2(P,C)-Ph2PCH2CH(PR ’Ph2)CH2}][BPh4] (R ’ = Me (23 a), Ph (24 a)).