The dimolybdenum thioxanthate complexes, Mo2(S2CSR)4, R = -C2H5, -iC3H7, -tC4H9, and -CH2C6H5, were synthesized and chemically characterized as analogues of the previously reported Mo2(S2COR)4 complexes. A series of complexes Mo2(S2CX)4, X = -SR, -OR, -NR2 and -R, was prepared and found to be electrochemically active. The primary cathodic process is analogous in all systems, and the effects of substituents on the redox couple are analyzed. The overall electrochemical behavior of the dimolybdenum(II) thioxanthate complexes is related to that of the oxo-bridged dimer Mo2O3(S2CSR)4. The interrelationship of the Mo2(S2CNR2)4 complex and the rearranged "carbene" derivative, Mo2S2(SCNR2)2(S2CNR2)2, is discussed.