The First Example of a Seven-Coordinate Vanadium(III) Thiolate Complex Containing the Hydrazine Molecule, an Intermediate of Nitrogen Fixation

The first example of a seven-coordinate vanadium(III) thiolate complex, [V(PS3ʹ ʹ)(N2H4)3] (1), where PS3ʹ ʹ = [P(C6H3-3-Me3Si-2-S)3] 3-, has been synthesized and characterized. Compound 1 contains a tetradentate ligand (PS3ʹ ʹ) and three hydrazine molecules, forming a capped octahedral geometry. A five-coordinate vanadium(III) complex, [V(PS3)(1-Me-Im)] (2), where PS3 = [P(C6H4-2-S)3]3and 1-Me-Im = 1-methyl-imidazole, was also obtained. Compound 2 adopts a trigonal bipyramidal geometry, in which the vanadium is ligated by the title ligand, PS3, and one 1-Me-Im molecule.