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Novel reactions of cationic carbyne complexes of manganese and rhenium with polymetal carbonyl anions. An approach to trimetal bridging carbyne complexes

The reaction of a cationic carbyne complex of manganese, [(η-C5H5)(CO)2Mn≡CC6H 5]BBr4 (1), with [(Ph3P)2N]2[Ru3(CO)11] (3) in THF at low temperature gave the heteronuclear trimetal bridging carbyne complex [MnRu2(μ-H)(μ-CO)2(μ3-CC6H 5)(CO)6(η-C5H5)] (7). A cationic carbyne complex of rhenium, [(η-C5H5)(CO)2Re≡CC6H 5]BBr4 (2), reacts similarly with 3, affording the corresponding bridging carbyne complex [ReRu2(μ-H)(μ-CO)2(μ3-CC6H 5)(CO)6(η-C5H5)] (8) and neutral Re-carbyne dimer [Re(CO)2(η-C5H5)(μ-CC6H5 )]2 (9). The compound [(Ph3P)2N]2[Os3(CO)11] (4) only reacts with 1 to give the trimetal bridging carbyne complex [MnOs2(μ-H)(μ-CO)2(μ3-CC6H 5)(CO)6(η-C5H5)] (10) and neutral Mn-carbyne dimer [Mn(CO)2(η-C5H5)(μ-CC6H5 )]2 (11). [(Ph3P)2N]2[Fe4(CO)13] (5) also reacts with cationic carbyne complexes 1 and 2 to give the trimetal bridging carbyne complexes [MnFe2(μ-H)(μ-CO)2(μ3CC6H 5)(CO)6(η-C5H5)] (12) and [ReFe2(μ-H)(μ-CO)2(μ3-CC6H 5)(CO)6(η-C5H5)] (13), respectively. Product 13, when treated with an excess of PPh3, gave the PPh3-substituted bridging carbyne complex [ReFe2(μ-H)(μ-CO)2(μ3-CC6H 5)(CO)5(PPh3)(η-C5H5) ] (14). In contrast to carbonylmetal anions 3-5, [Mo(η-C5H5)2(H)CO][Mn3(CO)9 (μ-SC6H5)4] (6) reacts with 1 to produce not the analogous bridging carbyne complexes but rather the mercapto-carbene complex [(ηC5H5)(CO)2Mn=C(SC6H5 )C6H5] (15) and the thiolato-bridged Mo-Mn carbonyl complex [Mo(η-C5H5)(CO)2(μ-SC6H5 )2Mn(CO)3] (16), while the analogous reaction of 2 with 6 yields the mercaptocarbene complex [(η-C5H5)(CO)2Re=C(SC6H5 )C6H5] (17) and phenylcarbene complex [(η-C5H5)(CO)2Re=C(H)C6H5 ] (18). The structures of 7, 9, 13, 14, and 16 have been established by X-ray diffraction studies.