Octahedral Zirconium Salan Catalysts for Olefin Polymerization: Substituent and Solvent Effects on Structure and Dynamics.

Group 4 metal-Salan olefin polymerization catalysts typically have relatively low activity, being slowed down by a pre-equilibrium favoring a non-polymerization active resting state identified as a isomer (MM); formation of the polymerization active species (FF) requires isomerization. We now show that the chemistry is more subtle than previously realized. Salan variations bearing large, flat substituents can achieve very high activity, and we ascribe this to the stabilization of the FF isomer, which becomes in energy than MM. Detailed in situ NMR studies of a fast (-anthracenyl) and a slow (-Bu) Salan precursors, suitably activated, indicate that preferred isomers in solution are different: the fast catalyst prefers FF while the slow catalyst prefers a highly distorted MM geometry. Crystal structures of the -anthracenyl substituted complex with a moderately (chlorobenzene) and, more importantly, a weakly coordinating solvent (toluene) in the first coordination sphere emphasize that the active FF isomer is preferred, at least for the benzyl species. Site epimerization (SE) barriers for the fast catalyst (Δ > 0, dissociative) and the slow catalyst (Δ < 0, associative) in toluene corroborate the solvent role. Diagnostic NMe C chemical shift differences allow unambiguous detection of FF or MM geometries for seven activated catalysts in different solvents, highlighting the role of solvent coordination strength and bulkiness of the -substituent on the isomer equilibrium. For the first time, active species of Zr-Salan catalysts were speciated. The slow catalyst is effectively trapped in the inactive MM state, as previously suggested. Direct observation of fast catalysts is hampered by their high reactivity, but the product of the first 1-hexene insertion maintains its FF geometry.