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

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