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Halide-Free Diarylcalcium Complexes-Syntheses, Structures, and Stability

机译:不含卤化物的二芳基钙配合物-合成,结构和稳定性

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A general procedure was developed for the synthesis of diarylcalcium complexes by addition of KOtBu to arylcalcium iodides in THF. Intermediate arylcalcium tert-butanolate dismutates immediately leading to insoluble tert-butanolate precipitates of calcium. Depending on the steric demand and denticity of additional neutral aliphatic azabases, mononuclear or dinuclear complexes trans-[Ca(α-Naph)2- (thf)_4] (1), [Ca(β-Naph)_2(thf)_4] (2), [Ca(Tol)_2(tmeda)]_2 (3), [Ca(Ph)_2(tmeda)]_2 (4), [Ca(Ph)_2(pmdta)(thf)] (5), [Ca(hmteta)(Ph)_2] (6), and [Ca([18]C-6)(Ph)_2] (7) were isolated (Naph=naphthyl; meda=N,N,N',N'-tetramethylethylenediamine; pmdta= N,N,N',N″,N″-pentamethyldiethylenetriamine; hmteta=N,N,N',N″,N″′,N″′-hexamethyltriethylenetetramine). The Ca-C bond lengths vary between 250.8 and 263.5 pm, the ipso-carbon atoms show low-field-shifted resonances in the ~(13)C NMR spectra.
机译:通过将KOtBu加到THF中的碘化芳基钙上,开发了一种合成二芳基钙络合物的通用方法。中间芳基叔丁醇盐钙立即发生歧化,导致钙的不溶叔丁醇盐沉淀。根据空间需求和其他中性脂族氮杂碱基的密度,单核或双核复合物反式-[Ca(α-Naph)2-(thf)_4](1),[Ca(β-Naph)_2(thf)_4] (2),[Ca(Tol)_2(tmeda)] _ 2(3),[Ca(Ph)_2(tmeda)] _ 2(4),[Ca(Ph)_2(pmdta)(thf)](5) ,[Ca(hmteta)(Ph)_2](6)和[Ca([18] C-6)(Ph)_2](7)分离出来(萘酚=萘基;甲基= N,N,N', N′-四甲基乙二胺; pmdta = N,N,N′,N″,N″-五甲基二亚乙基三胺; hmteta = N,N,N′,N″,N″′,N″′-六甲基三亚乙基四胺)。 Ca-C键的长度在250.8至263.5 pm之间变化,ipso-碳原子在〜(13)C NMR光谱中显示出低场移共振。

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