Zinc Complexes with the Chelating Amido‐Imino Ligand [1‐ n ‐Butyl‐2‐(2,6‐diisopropylphenyl)iminoacenaphthen‐1‐yl]‐2,6‐diisopropylphenylamide (L): Synthesis, Molecular Structure and Reactivity of [(L)ZnCl] 2 , (L)Zn‐ n Bu and (L)ZnN(SiMe 3 ) 2

Dimeric [(L)ZnCl] 2 ( 4 ) {L = [1‐ n ‐butyl‐2‐(2,6‐diisopropylphenyl)iminoacenaphthen‐1‐yl]‐2,6‐diisopropylphenylamide} was prepared by treatment of the lithium salt of the ligand (LLi) with equimolar amounts of anhydrous ZnCl 2 . Treatment of 4 with KN(SiMe 3 ) 2 affords the bis(trimethylsilyl)amido compound (L)ZnN(SiMe 3 ) 2 ( 5 ). The alkylzinc complex (L)Zn‐ n Bu ( 6 ) is the product of the reaction between the adduct LLi · n BuLi ( 3 ) and ZnCl 2 . Compounds 4 – 6 were characterized by 1 H 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 ). (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)