Activation and desoxygenation of CO, CO2, and SO2 with sulfur-rich azide and amide

The azide and amide complexes (NBu4)[Ni(N3)('S3')] (2) and (NBu4)[Ni[N(SiMe3)2]('S3')] (4) were found to react with CO, CO2, and SO2 under very mild conditions at temperatures down to -50 degrees C. Depending on the N oxidation state of the nitrogen ligands, addition or partial to complete desoxygenation of the oxides takes place. The reaction between 2 and CO gives (NBU4)[Ni(NCO)('S3')] (3). The reactions between 4 and CO, CO2, and SO2 afford selectively the cyano, isocyanato, and sulfinylimido complexes (NBu4)[Ni(X)('S3')] with X = CN- (5), NCO- (3), and NSO- (6). The silyl groups act as oxygen acceptors. Mechanisms are suggested which have in common the formation of reactive five-coordinate (NBu4)[Ni(L)(L')('S3')] intermediates. In these reactions, highly activated L and L' react with each other. The complexes were characterized by standard methods, and (NBu4)[Ni(CN)('S3')] (5) was also analyzed by X-ray crystallography.