κ3(P,C,C)-Allylphosphane Iridium(III) and Rhodium(III) Complexes: Preparation and Reactivity toward Nucleophilic Reagents

Abstract

The first allylphosphane iridium complexes [IrCl2(η5-C5Me5){κ(P)-R2PCH2CH═CH2}] (R = iPr (1a), Ph (1b)) have been synthesized by the reaction of the dimeric complex [IrCl(μ-Cl)(η5-C5Me5)]2 with allyldiisopropylphosphane (ADIP) and allyldiphenylphosphane (ADPP), respectively. The cationic complex [IrCl(η5-C5Me5){κ3(P,C,C)-iPr2PCH2CH═CH2}]+ (3+) has been prepared by the reaction of complex 1a with NaX (X = BPh4, PF6) in dichloromethane. The complex 3+ reacts with phosphanes and alkanethiolates to give the uncommon cationic complexes [IrCl(η5-C5Me5){κ2(P,C)-iPr2PCH2CH(PR2R′)CH2}]+ (5+–7+) and IrCl(η5-C5Me5){κ3(P,C,S)-iPr2PCH2CH(SR)CH2}]+ (13+ and 14+) by chemo- and regioselective addition of the nucleophiles to the π-olefin system. The reaction of 1a with LiBHEt3 gives the neutral complex [IrCl(η5-C5Me5){κ2(P,C)-iPr2PCH2CH2CH2}] (10). For comparative purposes, the synthesis of the complex [RhCl(η5-C5Me5){κ3(P,C,C)-iPr2PCH2CH═CH2}]+ (4+) and its reactivity with phosphanes, hydride, and thiolates has been also...