Dithiocarbamates of tungsten(III)and tungsten(IV)

Abstract

A series of dimeric tris(dialkyldithiocarbamato)tungsten(III) complexes, [W₂(S₂CNR₂)₆](R = Et, Prⁿ, or Buⁿ), and monomeric tetrakis(dialkyldithiocarbamato)tungsten(IV) complexes, [W(S₂CNR₂)₄], are described, including the analogous pentamethylenedithiocarbamate complexes. Electrochemical, spectroscopic, and magnetic studies show the tris series to be dimeric, probably with a binuclear seven-co-ordinate structure, whereas the tetrakis complexes are eight-co-ordinate and monomeric. The dimeric series are effective reducing agents in non-aqueous solvents for both pyridine N-oxide and tetraethylammonium nitrate with preservation of the binuclear structure, whereas [W(S₂CNEt₂)₄] is only effective with pyridine N-oxide.