Deprotonation of [(mu-H)Ir4(CO)10(mu-PPh2)], 1, gives [Ir4(CO)10(mu-PPh2)]- that reacts with Ph2PCCPh and CH3I to afford [Ir4(CO)8(CH3)(mu4-eta³-Ph2PCCPh)(mu-PPh2)], 2 (34%), besides [Ir4(CO)9(mu3-eta³-Ph2PC(H)CPh)(mu-PPh2)] and [(mu-H)Ir4(CO)9(Ph2PC<FONT FACE=Symbol>º</FONT>CPh)(mu-PPh2)]. Compound 2 was characterised by a single crystal X-ray diffraction analysis and exhibits a flat butterfly of metal atoms, with the Ph2PCCPh ligand interacting with all four Ir atoms and the methyl group bonded terminally to a wingtip Ir atom. Carbonylation of 2 yields initially (25 °C, 20 min) a CO addition product that, according to VT 31P{¹H} and 13C{¹H} studies, exists in solution in the form of two isomers 4A and 4B (8:1), and then (40 °C, 7 h), the CO insertion product [Ir4(CO)8{C(O)CH3}(mu4-eta³-Ph2PCCPh)(mu-PPh2)], 5. The molecular structure of 5, established by an X-ray analysis, is similar to that of 2, except for the acyl group that remains bound to the same Ir atom. The process is reversible at both stages. Treatment of 2 with PPh3 and P(OMe)3 affords the CO substitution products [Ir4(CO)7L(CH3)(mu4-eta³-Ph2PCCPh)(mu-PPh2)] (L = PPh3, 6 and P(OMe)3, 7), instead of the expected CO inserted products. According to the ¹H and 31P{¹H} NMR studies, the PPh3 derivative 6 exists in the form of two isomers (1:1) that differ with respect to the position of this ligand.
migratory insertion; iridium carbonyl clusters; alkyl clusters; carbonylation
