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(η5-Cyclopentadienyl or η5-pentamethylcyclopentadienyl)(1-phenylmethanimine-N,1-dithiolato)cobalt(III) (1) reacts with dimethyl acetylenedicarboxylate (DMAD) to give the adducts in which Co and S of the 1,2,5,3-cobaltadithiazole ring in the cobalt complex are bridged by 1,2-dimethoxycarbonylethylene-1,2-diyl groups (3a: the complex having Cp and 3b: the complex having Cp*). The sulfur atom adjacent to N is preferentially reacted. Photolysis of 3 gives 3,4-dimethoxycarbonyl-1,2,5-cobaltadithiolene (4) with the elimination of benzonitrile. In thermolysis in benzene, 3a undergoes selectively the elimination of benzonitrile to give 4a, while 3b undergoes the elimination of either DMAD or benzonitrile to give 1 or 4.

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