Structures of the anionic Mo/Co/S cluster salts [BnNMe(3)][Cp'2Mo2Co2S4(CO)2], [Na(15-crown-5)(1.5)][Cp*2Mo2Co2S4(CO)(2)], and [BnNMe(3)][Cp'2Mo2Co2S3(CO)(3)(SAr)] (Bn equals benzyl, Cp*=C(5)Me(4)Et, Ar=p-tolyl)

The paramagnetic cluster anions Cp'2Mo2Co2S4(CO)(2)(-) (6), and Cp*2Mo2Co2S4(CO)(2)(-)(6*) were prepared by the reaction of Cp'2Mo2Co2S3(CO)(4) with p-toluene thiolate or by Na amalgam reduction of the cubane Cp*2Mo2Co2S4(CO)(2) (Cp* = C(5)Me(4)Et), respectively. The GO-substituted cluster Cp'2Mo2Co2S3(CO)(3)(SAr)(-)(7) was a minor byproduct in the synthesis of 6. The X-ray crystal structures of these anionic clusters were determined. The effects of the addition or removal of electron density from the cluster core on the cluster structure is presented.