Abstract
Deprotonation of Ap*H {Ap*H = (2,6‐diisopropylphenyl)‐[6‐(2,4,6‐triisopropylphenyl)pyridin‐2‐yl]amine} and Ap'H {Ap'H = (2,6‐diisopropylphenyl)‐[6‐(2,6‐dimethylphenyl)pyridin‐2‐yl]amine} using KH leads to polymeric [Ap*K]~n~ and [Ap'K]~n~ which undergo clean salt metathesis reactions with NdCl~3~ in THF forming [Nd(Ap*)Cl~2~(THF)~2~]~2~ and [Nd(Ap')~2~‐Cl(THF)], respectively. Ethylene polymerization activities of the two chloro complexes (after activation with MAO) were studied. Derivatization of the chloro compounds proceeds without ate complex formation, for instance the reaction of [Nd(Ap')~2~Cl(THF)] with one equiv. of [K{N(SiMe~3~)~2~}] leads to the “THF‐free” silylamide [Nd(Ap')~2~{N(SiMe~3~)~2~}]. Furthermore rare examples of heteroleptic amido‐iodo complexes of selected divalent lanthanides can be stabilized by deprotonated Ap*H. Reaction of [Ap*K]~n~ with [LnI~2~(THF)~3~] (Ln = Yb, Sm) in THF leads, after workup in hexane, to [Yb(Ap*)I‐(THF)~2~]~2~ and [Sm(Ap*)I(THF)~2~]~2~. All lanthanide complexes, four of them are paramagnetic, were characterized by X‐ray crystal structure analysis. These compounds exhibit an excellent solubility in nonpolar solvents like hexane. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)