Abstract
The reaction of a sterically bulky β-diketiminato lithium complex [Li(ButNacnac)] (ButNacnac = [{N(Dip)C(But)}2CH]−, Dip = C6H3Pri2-2,6) with GeCl2·dioxane has given the germanium(II) chloride complex [(ButNacnac)GeCl] (3). Both it and its known tin analogue, [(ButNacnac)SnCl] (4), were crystallographically characterized and found to be monomeric in the solid state. The reduction of both complexes with elemental lithium in THF led to lithium complexes of N-heterocyclic germylidenide and stannylidenide anions, viz., [(THF)Li{η5-EC(But)C(H)C(But)N(Dip)}] (E = Ge, 5; Sn, 6). The reduction of the germanium(II) precursor, 3, also afforded the germanium(II) amide complex [(ButNacnac)Ge{N(H)(Dip)}] (7). The mechanisms of formation of the complexes are thought to involve a number of steps, including reductive ring contraction reactions. The crystallographic and spectroscopic data for [(THF)Li{η5-EC(But)C(H)C(But)N(Dip)}] indicate a significant degree of aromatic π-delocalization within their heterocycles.
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