Zinc complexes with the Chelating amido-imino ligand [1-n-butyl-2-(2,6-diisopropylphenyl)iminoacenaphthen-1-yl]-2,6-diisoprop ylphenylamide (L): Synthesis, molecular structure and reactivity of [(L)ZnCl](2), (L)Zn-nBu and (L)ZnN(SiMe3)(2)

摘要

Dimeric [(L)ZnCl](2) (4) (L = [1-n-butyl-2-(2,6-diisopropylphenyl)iminoacenaphthen-1-yl]-2,6-diisoprop ylphenyl-amide) was prepared by treatment of the lithium salt of the ligand (LLi) with equimolar amounts of anhydrous ZnCl2. Treatment of 4 with KN(SiMe3)(2) affords the bis(trimethyl-silyl)amido compound (L)ZnN(SiMe3)(2) (5). The alkylzinc complex (L)Zn-nBu (6) is the product of the reaction between the adduct LLi-nBuLi (3) and ZnCl2. Compounds 4-6 were characterized by H-1 NMR and IR spectroscopy. The molecular structures of 4 and 6 were determined by single-crystal X-ray analysis. In the solid state, the molecules of 4 exist as centrosymmetric, heterochiral dimers bridged by chlorine atoms, while compound 6 consists of monomeric molecules with three-coordinate zinc atoms. The reactions of 6 with tert-butanol, adamanthanol, 2,5-di-tert-butylaniline and diphenylacetonitrile do not proceed with alkane elimination but with protonation of the ligand affording the amino-imine LH (7).