Unusual Reactions of Cationic Carbyne Complexes of Manganese and Rhenium with the Carbonylmetal Anions [Ir(CO)4]-and [Ru(CO)4]2-. Novel Route to Heteropolymetallic Bridging Carbyne Complexes

The reaction of a cationic carbyne complex of manganese, [(η 5 -C 5 H 5 )(CO) 2 Mn⋮CC 6 H 5 ]BBr 4 ( 1 ), with [(Ph 3 P) 2 N][Ir(CO) 4 ] ( 3 ) in THF at low temperature gives a novel Mn 2 −Ir 2 mixed-tetrametal bridging carbyne complex with μ and μ 3 bridging carbyne ligands, [Mn 2 Ir 2 (μ-CC 6 H 5 )(μ 3 -CC 6 H 5 )(μ-CO) 3 (CO) 3 (η 5 -C 5 H 5 ) 2 ] ( 5 ), and a related Mn 2 −Ir 2 mixed-tetranuclear cluster with a μ bridging carbene ligand and a μ 3 bridging carbyne ligand, [Mn 2 Ir 2 {μ-C(CO)C 6 H 5 }(μ 3 -CC 6 H 5 )(μ-CO) 3 (CO) 4 (η 5 -C 5 H 5 ) 2 ] ( 6 ). A cationic carbyne complex of rhenium, [(η 5 -C 5 H 5 )(CO) 2 Re⋮CC 6 H 5 ]BBr 4 ( 2 ), reacts similarly with 3 to afford the corresponding Re 2 −Ir 2 mixed-tetrametal cluster [Re 2 Ir 2 {μ-C(CO)C 6 H 5 }(μ 3 -CC 6 H 5 )(μ-CO) 3 (CO) 4 (η 5 -C 5 H 5 ) 2 ] ( 8 ) and a novel Re−Ir 2 mixed-trimetal bridging carbyne complex with an allyl ligand, [ReIr 2 (μ-η 1:η 2 -C 3 H 5 )(μ 3 -CC 6 H 5 )(μ-CO) 2 (CO) 4 (η 5 -C 5 H 5 )] ( 7 ). The cationic carbyne complex 1 also reacts with the anionic compound Na 2 [Ru(CO) 4 ] ( 4 ) to give a heterotrimetal bridging carbyne complex with a μ-H ligand, [MnRu 2 (μ-H)(μ-CO) 2 (μ 3 -CC 6 H 5 )(CO) 6 (η 5 -C 5 H 5 )] ( 10 ), and the manganese aminocarbene complex [(η 5 -C 5 H 5 )(CO) 2 Mn C(C 6 H 5 )NH 2 ] ( 11 ), while the analogous reaction of the cationic carbyne complex 2 with 4 produces a novel Re 2 −Ru 2 mixed-tetrametal cluster with a μ 3 -C(CC 6 H 5 )(μ-CC 6 H 5 ) bridging carbene ligand, [Re 2 Ru 2 {μ 3 -C(CC 6 H 5 )(μ-CC 6 H 5 )}(μ-CO)(CO) 8 (η 5 -C 5 H 5 ) 2 ] ( 13 ), in addition to the corresponding heterotrimetal bridging carbyne complex [ReRu 2 (μ 3 -CC 6 H 5 )(μ-H)(μ-CO) 2 (CO) 6 (η 5 -C 5 H 5 )] ( 12 ) and aminocarbene complex [η 5 -C 5 H 5 (CO) 2 Re C(C 6 H 5 )NH 2 ] ( 14 ). The structures of complexes 6, 7, 11, 13, and 14 have been established by X-ray diffraction studies.