Exploration of Homogeneous Ethylene Dimerization Mediated by Tungsten Mono(imido) Complexes

Abstract

In combination with EtAlCl2, complexes {[WCl3(μ-Cl)(N-2,6-iPr2C6H3)]2}, [WCl4(NR)(thf)] (R = Et, iPr, cHx, Ph, 2,6-iPr2C6H3, 4-F-C6H4, and 2,4,6-F3-C6H2), and [WCl2(NR′)(PMe3)3] (R′ = Ph, 2,6-iPr2C6H3) were all productive ethylene dimerization pre-catalysts, giving turnover numbers (TONs) in the range of 400–144 000 (mol C2H4)(mol W)−1 and moderate selectivities toward 1-butene (>66%) depending on the nature of the imido substituent. The formation of C6 side-products resulted from the incorporation of 1-butene rather than direct trimerization, something that is independent of butene concentration. Stoichiometric reactions between the tungsten mono(imido) complexes and alkylaluminum reagents are described, which are consistent with the reduction of the tungsten centre playing an important part in the initiation process. Testing discrete WV and WIV mono(imido) complexes for olefin dimerization revealed the former to be significantly more active, which offers insight into the mode of action of the commercially relevant tungsten mono(imido)-selective dimerization initiators described herein.