Two types of substitution reactions occur between arylnitrene from aryl azides (1) and a cobaltadithiolene, (η5-cyclopentadienyl)(1,2-dicyano-1,2-ethenedithiolato)cobalt(III): 1) replacements of S by arylimino groups and 2) replacements of S–CX=CX moiety of a cobaltadithiolene by a biradical form of nitrene to give (η5-cyclopentadienyl)(2-imino-κN-arene-1-thiolato-κS)cobalt(III) (5). The reaction of 1 with a cluster compound [Cp4Co4S6] gives also 5.
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