Tp*WIVO(S2CNEt2): the Missing Member of the Series

Abstract

The missing member of the series Tp*ME(S₂CNEt₂) (M = Mo, W; E = O, S), namely Tp*WO(S₂CNEt₂), has been synthesized by oxygen-atom transfer from pyridine N-oxide to Tp*W(S₂CNEt₂)(CO)₂. The air-stable, blue-purple complex was characterized by microanalysis, mass spectrometry (m/z 645 (100%), [M]⁺), cyclic voltammetry, and IR and ¹H NMR spectroscopy. Solutions of the complex are dichroic and solvatochromic. The X-ray crystal structure of the complex revealed a six-coordinate, distorted octahedral complex with axial oxo (W = O 1.680(5) Å), ‘equatorial’ dithiocarbamate (W—S 2.3962(17) and 2.4102(17) Å), and facial tridentate Tp* ligands. The synthesis and characterization of Tp*WCl₃ are also reported.