The synthesis and characterization of new zirconium permethylpentalene
(form)amidinate complexes are described: Pn*Zr{N(Dipp)2CH}Cl (1), Pn* = η8-C8Me6 and Dipp = 2,6-
i
Pr-C6H3; [Pn*Zr{N(p-tol)2CH}Cl]2 (2), p-tol = 4-Me-C6H4; [Pn*Zr{N(
i
Pr)2CMe}Cl]2 (3); Pn*Zr{N(
i
Pr)2CPh}Cl (4); Pn*Zr{N(4-Me-C6H4)2CH}2 (5);
[Pn*Zr{N(
i
Pr)2CCH2}]2 (6); and Pn*Zr{N(
i
Pr)2CPh}(O-2,6,-Me-C6H3) (7). The monohalide derivatives 1–4 demonstrate
considerable structural diversity as the nature of the (form)amidinate-supporting
ligand is changed. While complexes with acidic backbone protons proved
susceptible to deprotonation using mild bases, those without underwent
straightforward salt metathesis reactions with alkali metal salts,
leading to complexes [Pn*Zr{N(
i
Pr)2CCH2}]2 (6) and Pn*Zr{N(
i
Pr)2CPh}(O-2,6-Me-C6H3) (7). Preliminary slurry-phase ethylene
polymerization studies are also reported using complexes 2, 4, 5, and 7 to gain a direct
comparison to the highly active, yet electronically saturated, Pn*Zr(CpR)Cl catalyst family.
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