Molecular and supported Ti(iii)-alkyls: efficient ethylene polymerization driven by the π-character of metal–carbon bonds and back donation from a singly occupied molecular orbital

Abstract

While Ti(III) alkyl species are the proposed active sites in Ziegler–Natta ethylene polymerization catalysts, the corresponding well-defined homogeneous catalysts are not known. We report that well-defined neutral β-diiminato Ti(III) alkyl species, namely [Ti(nacnac)(CH₂^tBu)₂] and its alumina-grafted derivative [(Al_sO)Ti(nacnac)(CH₂^tBu)], are active towards ethylene polymerization at moderate pressures and temperatures and possess an electron configuration well-adapted to insertion of ethylene. Advanced EPR spectroscopy showed that ethylene insertion into a Ti(III)–C bond takes place during polymerization from Ti(nacnac)(CH₂^tBu)₂. A combination of pulsed EPR spectroscopy and DFT calculations, based on a crystal structure of [Ti(nacnac)(CH₂^tBu)₂], enabled us to reveal details about the structure and electronic configurations of both molecular and surface-grafted species. For both compounds, the α-agostic C–H interaction, which involves the singly occupied molecular orbital, indicates a π character of the metal–carbon bond; this π character is enhanced upon ethylene coordination, leading to a nearly barrier-less C₂H₄ insertion into Ti(III)–C bonds after this first step. During coordination, back donation from the SOMO to the π*(C₂H₄) occurs, leading to stabilization of π-ethylene complexes and to a significant lowering of the overall energy of the C₂H₄ insertion transition state. In d¹ alkyl complexes, ethylene insertion follows an original “augmented” Cossee–Arlman mechanism that involves the delocalization of unpaired electrons between the SOMO, π*(C₂H₄) and σ*(Ti–C) in the transition state, which further favors ethylene insertion. All these factors facilitate ethylene polymerization on Ti(III) neutral alkyl species and make d¹ alkyl complexes potentially more effective polymerization catalysts than their d⁰ analogues.