Alkali metal compounds of a gallium(I) carbene analogue {:Ga[N(Ar)C(Me)]₂} (Ar = 2,6-ⁱPr₂C₆H₃)

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• 作者：Yanyan Liu^a ; Shaoguang Li^a ; Xiao-Juan Yang^a ; ^{yangxj@lzb.ac.cn} ; Qian-Shu Li^b ; Yaoming Xie^c ; Henry F. Schaefer^c ; Biao Wu^a ; ^d
• 关键词：Gallium(I) ; NHCs analogue ; Alkali metals ; Ga– ; M bond
• 刊名：Journal of Organometallic Chemistry
• 出版年：2011
• 出版时间：1 April 2011
• 年：2011
• 卷：696
• 期：7
• 页码：1450-1455
• 全文大小：664 K

文摘

A gallium dichloro complex (L⁻)Ga^IIICl₂ (1) with an α-diimine ligand [(2,6-ⁱPr₂C₆H₃)NC(Me)]₂ (L⁰ represents the neutral ligand, L⁻ is the radical-anionic form of the ligand, and L represents its dianion L²⁻) was used to synthesize a series of alkali metal complexes of an N-heterocyclic carbenes (NHCs)-like gallium(I) species. Reduction of the precursor 1 with three equivalents of Na, Li, K or KC₈, respectively, in THF gave the complexes [LGa^INa(THF)₃] (2), [LGa^ILi(THF)₃] (3), [LGa^I{μ₂-K(THF)₄}Ga^IL][K(THF)₆] (4) and [LGa^I(μ₂-K){μ₂-K(THF)₂}Ga^IL] (5). In these complexes, the original radical-anionic ligand was further reduced to the dianion, whereas the Ga^III ion was reduced to Ga^I to yield the NHCs analogue [:GaN₂C₂]⁻, which then coordinated to alkali metal ions to form the complexes 2–5. Single crystal X-ray diffraction analyses revealed that these complexes feature direct Ga–M bonds (M = Li, Na, and K), which have also been studied by DFT computations.