Unusual ligand formation in carbon disulfide chemistry: synthesis, structure, and reactivity of Mo2(S2CNEt2)3(.mu.-CSC(S)S)(.mu.-S3C2NEt2)

The complex reaction of CS/sub 2/ with Mo(CO)/sub 2/(S/sub 2/CNEt/sub 2/)/sub 2/ in the presence of 2 equiv of triphenylphosphine forms the dinuclear complex Mo/sub 2/(S/sub 2/CNEt/sub 2/)/sub 3/(..mu..-CSC(S)S)(..mu..-S/sub 3/C/sub 2/NEt/sub 2/) (1) in 95% yield. The identity of 1 was determined by a single-crystal X-ray study. Two molecules of 1 crystallize in space group P1 with a = 15.749 (6) A, b = 16.013 (7) A, c = 9.740 (6) A, ..cap alpha.. = 107.26 (3)/sup 0/, ..beta.. = 105.92 (4)/sup 0/, and ..gamma.. = 71.14 (2)/sup 0/. The similarity of the structure of 1 to that of Mo/sub 2/(..mu..-S)(..mu..-EtC identical with CEt)(S/sub 2/CNMe/sub 2/)/sub 3/(SCNMe/sub 2/)(4) encourages development of a qualitative molecular orbital scheme for 1 from the analysis presented for the dinuclear alkyne derivative 4. Both of these dinuclear compounds have formal Mo(III) centers in roughly conlateral-biotahedral geometries. Addition of Me/sup +/ using the (Me/sub 3/O)(BF/sub 4/) reagent yields a cation that may be subsequently reduced with use of K(HB(O-i-Pr)/sub 3/). Cyclic voltammetry and visible spectroscopy data are compared for these dinuclear species. 30 references, 4 figures, 6 tables.