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

Abstract

The reaction of a cationic carbyne complex of manganese, [(η5-C5H5)(CO)2Mn⋮CC6H5]BBr4 (1), with [(Ph3P)2N][Ir(CO)4] (3) in THF at low temperature gives a novel Mn2−Ir2 mixed-tetrametal bridging carbyne complex with μ and μ3 bridging carbyne ligands, [Mn2Ir2(μ-CC6H5)(μ3-CC6H5)(μ-CO)3(CO)3(η5-C5H5)2] (5), and a related Mn2−Ir2 mixed-tetranuclear cluster with a μ bridging carbene ligand and a μ3 bridging carbyne ligand, [Mn2Ir2{μ-C(CO)C6H5}(μ3-CC6H5)(μ-CO)3(CO)4(η5-C5H5)2] (6). A cationic carbyne complex of rhenium, [(η5-C5H5)(CO)2Re⋮CC6H5]BBr4 (2), reacts similarly with 3 to afford the corresponding Re2−Ir2 mixed-tetrametal cluster [Re2Ir2{μ-C(CO)C6H5}(μ3-CC6H5)(μ-CO)3(CO)4(η5-C5H5)2] (8) and a novel Re−Ir2 mixed-trimetal bridging carbyne complex with an allyl ligand, [ReIr2(μ-η1:η2-C3H5)(μ3-CC6H5)(μ-CO)2(CO)4(η5-C5H5)] (7). The cationic carbyne complex 1 also reacts with the anionic compound Na2[Ru(CO)4] (4) to give a heterotrimetal bridging carbyne complex with a μ-H ligand, [MnRu2(μ-H)(μ-CO)2(μ3-CC6H5)(CO)6(η5-C5H5)] (10), and the manganese aminocarbene complex [(η5-C5H5)(CO)2MnC(C6H5)NH2] (11), while the analogous reaction of the cationic carbyne complex 2 with 4 produces a novel Re2−Ru2 mixed-tetrametal cluster with a μ3-C(CC6H5)(μ-CC6H5) bridging carbene ligand, [Re2Ru2{μ3-C(CC6H5)(μ-CC6H5)}(μ-CO)(CO)8(η5-C5H5)2] (13), in addition to the corresponding heterotrimetal bridging carbyne complex [ReRu2(μ3-CC6H5)(μ-H)(μ-CO)2(CO)6(η5-C5H5)] (12) and aminocarbene complex [η5-C5H5(CO)2ReC(C6H5)NH2] (14). The structures of complexes 6, 7, 11, 13, and 14 have been established by X-ray diffraction studies.