SYNTHESIS, STRUCTURE AND ELECTROCHEMICAL STUDIES ON SINGLE MoFe3S4 AND WFe3S4 CUBANE-TYPE CLUSTER COMPOUNDS

Single cubane-like clusters, MFe3S4（R2dtc）5 （M=Mo, R2=—（CH2）4—, Bz2; M=W, R2=Me2, —（CH2）4—; dtc=dialkyldithiocarbamate） were synthesized by assembly reaction of （NH4）2MS4 （M=Mo, W）, FeCl2 with R2dtcNa （or NH4） in DMF. The structure, IR, EPR and cyclic voltammogram are described and discussed. MoFe3S4（C4H8dtc）5 was also obtained from the conversion of linear cluster Fe（DMF）6[（FeCl2）2MoS4] in the presence of C4H8dtc NH4. Both clusters MoFe3S4（C4H8dtc）4·2C2H5CN and WFe3S4（C4H8dtc）5·2DMF crystallize in the monoclinic space group C2/c with a=12.544（2）, （Mo-cluster）, 12.533（4） （W-cluster）; b=20.478（4）, 20.121（6）; c=19.582（7）, 19.659（2）;β=102.82（2）, 102.96（3）°; and Z=4, 4. Their structures were refined to R=0.057 and 0.064 with use of 2690 and 2179 reflections （ι>3Q（I））, respectively. Many similarities in structure for Mo and W clusters indicate that both Mo and W play a very similar role in the clusters.