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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Amine mediated proton transfer reaction and C-Cl bond activation of solvent chloroform by a trinuclear copper(II) complex of a glucopyranosylamine derived ligand
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Amine mediated proton transfer reaction and C-Cl bond activation of solvent chloroform by a trinuclear copper(II) complex of a glucopyranosylamine derived ligand

机译：氨基吡喃葡萄糖胺衍生的配体的三核铜（II）络合物的胺介导的质子转移反应和溶剂氯仿的C-Cl键活化

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摘要

An amine mediated C-Cl bond activation process of the solvent chloroform has been explored by a coordinatively labile trinuclear Cu(II) complex, [Cu-3(L-1)(2)(MeOH)(H2O)] (1), derived from N-(3-tert-butyl-2-hydroxybenzylidene)-4,6-O-ethylidene-beta-D-glucopyranosylamine (H3L1). The effect of activation is extremely high with methylamine, resulting in the formation of [Cu(MeNH2)(5)]Cl-2 ( 2) and [Cu(L-2)(2)] (3; HL2 = 2-tert-butyl-6-[(methylimino)methyl]phenol), however, under identical conditions it is moderate with ethylamine resulting in the isolation of crystals of the intermediate amine bound trinuclear copper(II) complex, [Cu-3(L-1)(2)(EtNH2)(2)(MeOH)(2)] ( 5), which was further converted into the mononuclear complex, [Cu(HL1)(EtNH2)] ( 6), in a novel crystal- to- crystal transformation. The successive isolation of the ethylamine-bound tri- and mononuclear complexes, 5 and 6, supported the occurrence of proton transfer reactions, which might be a key step in C - Cl bond activation. The primary and secondary amines, 2-aminomethylpyridine, N, N'-dimethylethylenediamine, and 1,4,7-triazacyclononane, also having chelating features further enhance the rate of activation. No activation has been noted in the case of triethylamine and N, N, N', N'-tetramethylethylenediamine. Formation of a carbene- trapped compound, 2,6- xylyl isocyanide, was con. rmed in the reaction of complex 1 with 1,4,7-triazacyclononane and 2,6-xylidine in CHCl3, suggesting that the C-Cl bond cleavage led to the generation of dichlorocarbene. In addition, the mononuclear complex 6 has been transformed into a homotrinuclear complex [Cu-3(L-1)(2)(MeOH)(2)] by treatment with Cu(II) ions in MeOH/ CHCl3, suggesting the possibility that the former could be regarded as a suitable metalloligand for heterotrimetallic complex synthesis.
机译：已通过协调不稳定的三核Cu（II）配合物[Cu-3（L-1）（2）（MeOH）（H2O）]探索了胺介导的溶剂氯仿的C-Cl键活化过程。衍生自N-（3-叔丁基-2-羟基亚苄基）-4,6-O-亚乙基-β-D-吡喃葡萄糖胺（H3L1）。甲胺的活化作用极高，导致形成[Cu（MeNH2）（5）] Cl-2（2）和[Cu（L-2）（2）]（3; HL2 = 2叔-丁基-6-[[（甲基亚氨基）甲基]苯酚），但是，在相同的条件下，它与乙胺适中，导致中间胺结合的三核铜（II）配合物[Cu-3（L-1） ）（2）（EtNH2）（2）（MeOH）（2）]（5），在新的晶体-晶体结构中进一步转化为单核络合物[Cu（HL1）（EtNH2）]（6）。晶体转化。连续分离乙胺键合的三核和单核配合物5和6支持质子转移反应的发生，这可能是C-Cl键活化的关键步骤。伯胺和仲胺，2-氨基甲基吡啶，N，N'-二甲基乙二胺和1,4,7-三氮杂环壬烷也具有螯合特征，进一步提高了活化速率。在三乙胺和N，N，N′，N′-四甲基乙二胺的情况下，未发现活化。卡宾捕获的化合物2，6-二甲苯基异氰化物的形成是有利的。在配合物1与1,4,7-三氮杂环壬烷和2,6-二甲苯基在CHCl3中的反应中发现，这表明C-Cl键断裂导致生成二氯卡宾。此外，通过在MeOH / CHCl3中用Cu（II）离子处理，单核络合物6已转化为同三核络合物[Cu-3（L-1）（2）（MeOH）（2）]，这表明可能前者可被认为是适合异三金属配合物合成的金属配体。

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