Reaction of VOCl3 with racemic trans-1,2-dithiacyclohexanediyl-2,2'-bis(6-tert-butyl-4-methylphenol) affords the chiral-at-metal vanadium(V) complex [V{(C6H2O-6-tert-Bu-4-Me)(2)S2C6H10}OCl] (1). The molecular structure of 1 was established by single crystal X-ray diffraction, which shows a cis-alpha configuration of the ligand around the vanadium center. Upon activation with MAO, 1 was found to be a highly active catalyst for the polymerization of ethylene, but was not active in the polymerization of propene and styrene. The influence of temperature and cocatalyst ratio on polymerization activity was studied. (C) 2008 Elsevier B.V. All rights reserved.