SYNTHESIS AND CHARACTERIZATION OF THE FORMAL NI(III) AND CU(III) COORDINATION-COMPLEXES OF THE NEW 1,2-DITHIOLENE, 1,4-BUTANEDIYLDITHIOETHYLENE-1,2-DITHIOLATE

The new 1,2-dithiolene, 1,4-butanediyldithioethylene-1,2-dithiolate, has been isolated. In addition, new monoanionic bis-complexes with nickel and copper have been prepared and isolated. The formal Ni(III) complex crystallizes in the orthorombic space group, P(bca), with a = 9.762(9), b = 12.53(2), and c = 23.166(3) angstrom, with 4 molecules in the unit cell. The structure was refined to an R = 9.01% (R(w) = 8.95%). The formal Cu(III) complex crystallizes in the monoclinic space groUP, C2/c, with a = 25.567(6), b = 8.011(3), c = 14.504(3) angstrom, and beta = 106.17(2)-degrees with 4 molecules in the unit cell. The structure refined to R = 4.2% with R(w) = 4.3%. Comparisons to similar 1,2-dithiolenes suggest this ligand produces only modest structural and electronic differences when compared to the 1,3-propanediyldithioethylene-1,2-dithiolate complexes. The oxidation (to a neutral complex) and reduction (to a dianion) for the Ni(III) and Cu(III) complexes show large differences from those of maleonitriledithiolate. Other physical data are presented as well.