Anisole−Diphenoxide Ligands and Their Zirconium Dichloride and Dialkyl Complexes

Abstract

Linear triphenol H3[RO3] (2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-R-phenol; R = Me, tBu) was found to undergo selective mono-deprotonation and mono-O-methylation. Deprotonation of H3[RO3] with 1 equiv of nBuLi resulted in the formation of Li{H2[RO3]}(Et2O)2 (R = Me (1a), tBu (1b)), in which the central phenol unit was lithiated. Treatment of H3[RO3] with methyl p-toluenesulfonate in the presence of K2CO3 in CH3CN gave the corresponding anisol-diphenol H2[RO2O] (2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-R-anisole; R = Me (2a), tBu (2b)). Reaction of H2[RO2O] with 2 equiv of nBuLi gave the dilithiated derivatives Li2[RO2O]. The lithium salts were reacted with ZrCl4 in toluene/THF to obtain the dichloride complex [RO2O]ZrCl2(thf) (R = Me (3a), tBu (3b)). 3b underwent dimerization along with a loss of THF to generate {[tBuO2O]ZrCl2}2 (4), whereas 4 was dissolved in THF to regenerate the monomer 3b. Alkylation of 3 with MeMgBr, PhCH2MgCl, and Me3SiCH2MgCl gave [MeO2O]ZrMe2(thf) (5), [RO2O]Zr(CH2Ph)2 (R = Me (6a), tBu (6b)), and [tBuO2O]Zr(CH2SiMe3)2 (7), respectively. Reaction of 3b with LiBHEt3 produced the hydride-bridged dimer [Li2(thf)4Cl]{[tBuO3]Zr}2(micro-H)3} (8), in which demethylation of the dianionic [tBuO2O] ligand took place to give the trianionic [tBuO3] ligand. The X-ray crystal structures of 1b, 2a, 3a, 4, 6a, and 7 were reported.