Synthesis and reactivity of the bulky germanium(IV) trisamide complexes BrGe[N(SiMe3)2]3 and LiGe[N(SiMe3)2]3:: X-ray crystal structures of BrGe[N(SiMe3)2]3 and [(Me3Si)2N]3Ge(CH2CH2CH2CH3)

The bulky germanium(IV) trisamide complex BrGe[N(SiMe3)(2)](3) has been prepared and structurally characterized. Reaction of this material with "BuLi resulted in [(Me3Si)(2)N](3)Ge(CH2CH2CH2CH3), which has also been structurally characterized, but no reaction with lithium metal was observed in the attempted preparation of LiGe[N(SiMe3)(2)](3). However, analytically pure LiGe[N(SiMe3)(2)](3) was prepared by the reaction of 3 equivalents of LiN(SiMe3)(2) with Gel, Evidence is presented that this germyllithium reagent is a major by-product in the synthesis of Ge[N(SiMe3)(2)](2) when the latter reagent is obtained from GeCl2 center dot (dioxane) prepared by the method of Kolesnikov et al. Reaction of the germyllithium reagent with 2,6-diphenylphenol yields the mixed Ge/Li cage complex [Li(mu(2)-OC6H3Ph2-2,6)(3)Ge], which had originally been obtained serendipitously via the reaction of 2,6-diphenylphenol with Ge[N(SiMe3)](2). (c) 2004 Elsevier B.V. All rights reserved.