Unusual Reactions of Cationic Carbyne Complexes of Manganese and Rhenium with Reactive Salts [Et3NH][(μ-CO)(μ-RS)Fe2(CO)6]. A Route to Dimetal Bridging Carbene Complexes

Abstract

The reaction of a cationic carbyne complex of manganese, [η-C5H5(CO)2Mn⋮CC6H5]BBr4 (1), with the reactive salt [Et3NH][(μ-CO)(μ-n-C4H9S)Fe2(CO)6] (3) in THF at low temperature gave the dimetal bridging carbene complex [MnFe{μ-C(n-C4H9S)C6H5}(CO)5(η-C5H5)] (8) and [Fe(CO)3(n-C4H9S)]2 (7). 1 reacted with [Et3NH][(μ-CO)(μ-C6H5S)Fe2(CO)6] (4) to give the bridging carbene complex [MnFe{μ-C(C6H5S)C6H5}(CO)5(η-C5H5)] (11) and the manganese phenylthiocarbene complex [η-C5H5(CO)2MnC(C6H5S)C6H5] (12), besides [Fe(CO)3C6H5S]2 (10). 1 also reacted with [Et3NH][(μ-CO)(μ-p-CH3C6H4S)Fe2(CO)6] (5) to yield [Fe(CO)3(p-CH3C6H4S)]2 (13) and the bridging carbene complex [MnFe{μ-C(p-CH3C6H4S)C6H5}(CO)5(η-C5H5)] (14). Analogous reactions of the cationic rhenium carbyne complex [η-C5H5(CO)2Re⋮CC6H5]BBr4 (2) with 3 and 4 gave the corresponding bridging carbene complexes [ReFe{μ-C(n-C4H9S)C6H5}(CO)5(η-C5H5)] (16) and [ReFe{μ-C(C6H5S)C6H5}(CO)5(η-C5H5)] (17) and the phenylthiocarbene complex [η-C5H5(CO)2ReC(C6H5S)C6H5] (18), respectively. The structures of 8, 11, 12, 16, and 18 have been established by X-ray diffraction studies.