Remarkable Reactions of Cationic Carbyne Complexes of Manganese and Rhenium with Na[Fe(CO)4CN] and Et4N[Mn(CO)4(CN)2

Abstract

The reaction of a cationic carbyne complex of manganese, [(η-C5H5)(CO)2Mn⋮CC6H5]BBr4 (1), with Na[Fe(CO)4CN] (3) in THF at low temperature gives the phenyl(tetracarbonylcyanoiron)carbene−manganese complex [(η-C5H5)(CO)2MnC(C6H5)NCFe(CO)4] (5). The analogous reaction of a cationic carbyne complex of rhenium, [(η-C5H5)(CO)2Re⋮CC6H5]BBr4 (2), with 3 affords the corresponding carbene−rhenium complex [(η-C5H5)(CO)2ReC(C6H5)NCFe(CO)4] (6). Complex 1 reacts with Et4N[Mn(CO)4(CN)2] (4) to yield the novel trinuclear metal dicarbene−manganese complex [{(η-C5H5)(CO)2MnC(C6H5)NC}2Mn(CO)3CN] (7) and the novel tetranuclear metal dicarbene−manganese complex [{(η-C5H5)(CO)2MnC(C6H5)NC}2Mn(CO)3CNMn(CO)2(η-C5H5)] (8). Complex 2 reacts similarly with 4 to afford the corresponding trinuclear dicarbene−rhenium complex [{(η-C5H5)(CO)2ReC(C6H5)NC}2Mn(CO)3CN] (9). The structures of complexes 5−9 have been established by X-ray crystallography.