Zirconium Permethylpentalene Amidinate Complexes: Characterization, Bonding, and Olefin Polymerization Catalysis

The synthesis and characterization of new zirconium permethylpentalene (form)amidinate complexes are described: Pn*Zr{N(Dipp)2CH}Cl (1), Pn* = ?8-C8Me6 Dipp 2,6-iPr-C6H3; [Pn*Zr{N(p-tol)2CH}Cl]2 (2), p-tol 4-Me-C6H4; [Pn*Zr{N(iPr)2CMe}Cl]2 (3); Pn*Zr{N(iPr)2CPh}Cl (4); Pn*Zr{N(4-Me-C6H4)2CH}2 (5); [Pn*Zr{N(iPr)2CCH2}]2 (6); Pn*Zr{N(iPr)2CPh}(O-2,6,-Me-C6H3) (7). monohalide derivatives 1–4 demonstrate considerable structural diversity as the nature (form)amidinate-supporting ligand is changed. While with acidic backbone protons proved susceptible to deprotonation using mild bases, those without underwent straightforward salt metathesis reactions alkali metal salts, leading (6) Pn*Zr{N(iPr)2CPh}(O-2,6-Me-C6H3) Preliminary slurry-phase ethylene polymerization studies also reported 2, 4, 5, 7 gain a direct comparison highly active, yet electronically saturated, Pn*Zr(CpR)Cl catalyst family.