Syntheses of Ir 4 (CO) 6 (η 5 ‐C 5 Me 4 H) 2 and Ir 7 (μ 3 ‐CO) 3 (CO) 12 (η 5 ‐C 5 Me 5 ) from Pentametallic Molybdenum‐Iridium Cluster Precursors

Reaction of Mo 2 Ir 3 (μ‐CO) 3 (CO) 6 (η 5 ‐C 5 H 5 ) 2 (η 5 ‐C 5 Me 5 ) with Ir(CO) 2 (η 5 ‐C 5 Me 4 H) afforded the four‐valence‐electron‐deficient butterfly cluster Ir 4 (CO) 6 (η 5 ‐C 5 Me 4 H) 2 ; its stability has been rationalized with the aid of density functional theory calculations, which suggest that significant additional intracluster bonding alleviates the formal electron deficiency. Reaction of MoIr 4 (CO) 10 (η 5 ‐C 5 H 5 )(η 5 ‐C 5 Me 5 ) with [N(PPh 3 ) 2 ][Ir(CO) 4 ] afforded the capped octahedral cluster Ir 7 (μ 3 ‐CO) 3 (CO) 12 (η 5 ‐C 5 Me 5 ), which possesses three semi‐face‐capping CO ligands. These outcomes demonstrate that heterometallic clusters may serve as a potential source of new homometallic clusters following appropriate M–M′ cleavage.