Novel Reactions of Cationic Carbyne Complexes of Manganese and Rhenium with (Ph3P)2NW(CO)5NCO, (Ph3P)2NW(CO)5SCN, and NaW(CO)5CN

Abstract

The reaction of a cationic carbyne complex of manganese, [η-C5H5(CO)2Mn⋮CC6H5]BBr4 (1), with (Ph3P)2NW(CO)5NCO (3) in THF at low temperature gave the novel chelated carbene complex [η-C5H4(CO)2MnC(NHCO)C6H5] (6). The analogous reaction of a cationic carbyne complex of rhenium, [η-C5H5(CO)2Re⋮CC6H5]BBr4 (2), with 3 afforded the azametallacyclic complex [η-C5H5(CO)2ReC(C6H5)(CO)NW(CO)5] (7). The reaction between 1 and (Ph3P)2NW(CO)5SCN (4) led to the loss of a sulfur atom to give the phenyl(pentacarbonylisocyanotungsten)carbene−manganese complex [η-C5H5(CO)2MnC(C6H5)CNW(CO)5] (8). However, the reaction of 2 with 4 afforded the (isothiocyanato)phenylcarbene−rhenium complex [η-C5H5(CO)2ReC(C6H5)SCN] (9). Complexes 1 and 2 react with NaW(CO)5CN (5) to produce novel phenyl(pentacarbonylcyanotungsten)carbene−manganese and −rhenium complexes, [η-C5H5(CO)2MnC(C6H5)NCW(CO)5] (10) and [η-C5H5(CO)2ReC(C6H5)NCW(CO)5] (11), respectively. The structures of 6, 7, 8, and 11 have been established by X-ray diffraction studies.