Ethylene oligomerization using nickel dithiolene complexes Ni(S2C2R2)2 (R = Ph, CF3) and the crystal structure of Ni[S2C2(CF3)2]2

Nickel bis(dithiolene) complexes have been known for over four decades, yet little is known regarding the chemistry of this important subclass of inorganic coordination complexes in olefin oligomerization or polymerization. We report here that Ni(S2C2R2)2 (R = Ph, CF3) are converted to active catalysts for ethylene oligomerization when activated with methylaluminoxane (MAO). The catalyst activity is comparable to some nickel coordination complexes with N-donor ligands under similar conditions. The products are mainly butenes and hexenes, with small amounts of higher oligomers. The product distribution pattern is consistent with a nickel hydride species being the active center, where fast β-hydride elimination limits the products to mostly butenes and hexenes. The exact nature of the active center and the reaction mechanism remain to be investigated. In addition, we determined the crystal structure for Ni[S2C2(CF3)2]2. The molecule crystallizes in the P21/n space group and adopts a planar geometry with expected bond lengths and angles. Comparing this structure with that for the donor–acceptor complex with perylene reveals elongation of both the Ni–S and the S–C bonds in the latter, suggesting reduction of Ni[S2C2(CF3)2]2 may have occurred in the latter.