Structures of the Anionic Mo/Co/S Cluster Salts [BnNMe₃][Cp‘₂Mo₂Co₂S₄(CO)₂], [Na(15-crown-5)1.5][Cp*₂Mo₂Co₂S₄(CO)₂], and [BnNMe₃][Cp‘₂Mo₂Co₂S₃(CO)₃(SAr)] (Bn = Benzyl, Cp* = C₅Me₄Et, Ar =p-Tolyl)

The paramagnetic cluster anions Cp‘ 2 Mo 2 Co 2 S 4 (CO) 2 - ( 6 ), and Cp* 2 Mo 2 Co 2 S 4 (CO) 2 - ( 6* ) were prepared by the reaction of Cp‘ 2 Mo 2 Co 2 S 3 (CO) 4 with p -toluene thiolate or by Na amalgam reduction of the cubane Cp* 2 Mo 2 Co 2 S 4 (CO) 2 (Cp* = C 5 Me 4 Et), respectively. The CO-substituted cluster Cp‘ 2 Mo 2 Co 2 S 3 (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.