AbstractThe electronic structures of six cubane‐like cluster compounds of the type [Fe4S4L4]n(L = SH, OH, and Cl,n=‐2 and −3; L=NO,n= 0 and −1) have been calculated by using DV‐Xαmethod, and the bonding properties are discussed with emphasis on the ligand effect on cluster bonding. The comparisons of MO energies and cluster charge distributions with the experimental data are made, and the differences between the early studies and the present one are also briefly