Transition metal complexes with sulfur ligands, part 146 activation and desoxygenation of CO, CO2, and SO2 with sulfur-rich azide and amide [Ni(L)(' S-3 ')] complexes (' S-3 '(2-)=bis(2-mercaptophenyl)sulphide (2-))

The azide and amide complexes (NBu4)[Ni(N-3)('S-3')] (2) and (NBu4)[Ni{N(Si Me3)(2)}('S-3')] (4) were found to react with CO, CO2, and SO2 under very m ild conditions at temperatures down to -50 degreesC. Depending on the N oxi dation state of the nitrogen ligands, addition or partial to complete desox ygenation of the oxides takes place. The reaction between 2 and CO gives (N Bu4)[Ni(NCO)('S-3')] (3). The reactions between 4 and CO, CO2, and SO2 affo rd selectively the cyano, isocyanato, and sulfinylimido complexes (NBu4)[Ni (X)('S-3')] with X=CN- (5), NCO- (3), and NSO- (6). The silyl groups act as oxygen accepters. Mechanisms are suggested which have in common the format ion of reactive five-coordinate (NBu4)[Ni(L)(L')('S-3')] intermediates. In these reactions, highly activated L and L' react with each other. The compl exes were characterized by standard methods, and (NBu4)[Ni(CN)('S-3')] (5) was also analyzed by X-ray crystallography.