Phosphorus–carbon bond formation via reactions of triphenylphosphine with acetylene and pentamethylcyclopentadienyl coordinated to iridium(III)

Phosphorus–carbon bond is formed via: (i) the apparent HCCH insertion into Ir–P bond to produce Ir–CHCH–PPh3 group and (ii) the activation of the ring-methyl group of the coordinated Cp* (C5Me5 −) to produce Ir(η5-C5Me4CH2–PPh3) group from reactions of iridium(III)–Cp* complexes, [Cp*IrL3]n+ (n=1, 2); Cp*=C5Me5 −; L3=Cl(PPh3)2 (3), (CH3CN)3 (5). The following new P–C bond containing iridium(III) complexes have been prepared: [Cp*Ir(–CHCH–PPh3)Cl(PPh3)]+ (4) from 3 with HCCH; [Ir(η5-C5Me4CH2–PPh3)(H)(PPh3)2]2+ (6) from 5 with PPh3; [Cp*Ir(–CHCH–PPh3)2(PPh3)]2+ (7) from 5 with HCCH and PPh3; [Ir(η5-C5Me4CH2–PPh3)(–CHCH–PPh3)Cl(PPh3)]2+ (8) from [Ir(η5-C5Me4CH2–PPh3)(Cl)(PPh3)2]2+ (6-Cl) with HCCH; [Ir(η5-C5Me3(1,3-CH2–PPh3)2(H)(PPh3)2)]3+ (10) from [Ir(η5-C5Me4CH2–PPh3)(NCCH3)2(PPh3)]3+ (9) with PPh3; [Ir(η5-C5Me4CH2–PPh3)(–CHCH–PPh3)2(PPh3)]3+ (11) from 9 with HCCH and PPh3.