S. Dagorne, S. Bellemin‐Laponnaz, C. Romain
Apr 26, 2013
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Organometallics
Abstract
Various zirconium and hafnium amido, chloro, and benzyl complexes supported by a tridentate N-heterocyclic carbene bis-phenolate dianionic ligand ((OCO)2–) have been synthesized and structurally characterized. The alcohol elimination reaction of the protio ligand N,N′-bis(2-hydroxy-3,5-di-tert-butylphenyl)-4,5-dihydroimidazolium chloride (1) and the metal alkoxide precursors M(OiPr)4(HOiPr) (M = Zr, Hf) and a subsequent alkoxide/chloride exchange reaction (upon addition of trimethylsilyl chloride, TMSCl) afforded the corresponding Zr and Hf carbene dichloro complexes as THF adducts: (OCO)MCl2(THF) (2a-THF, M = Zr; 2b-THF, M = Hf). As determined by single-crystal X-ray crystallographic studies, the molecular structure of the Hf derivative 2b-THF confirmed the proposed formulation and the effective formation of a (OCO)Hf chelate. In the case of Zr, an amine elimination reaction between protio ligand 1 and Zr(NMe2)4 yielded the corresponding Zr amido THF adduct (OCO)Zr(NMe2)(Cl)(THF) (3a-THF) when carried in...