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

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