Tetrahydrofuran in TiCl₄/THF/MgCl₂: a Non-Innocent Ligand for Supported Ziegler–Natta Polymerization Catalysts

While Ziegler–Natta (ZN) polymerization is one of the most important catalytic industrial processes, the atomic-scale nature of the catalytically active surface species remains unknown. Coupling high-resolution solid-state NMR spectroscopy with periodic density functional theory (DFT) calculations, we demonstrate that the major surface species in the ZN precatalyst corresponds to an alkoxy Ti­(IV) surface species, which probably results from the ring-opening of tetrahydrofuran (THF) on a cationic Ti­(IV) species.