| Abstrakt: |
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 SO2under very mild conditions at temperatures down to −50 °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 2and CO gives (NBu4)[Ni(NCO)(′S3′)] (3). The reactions between 4and CO, CO2, and SO2afford 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. |
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