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首页> 外文期刊>Zeitschrift fur Anorganische und Allgemeine Chemie >Reactivity of 2,2 '-Bis(2N-(1,1 ',3,3 '-tetramethyl-guanidino))diphenylene-amine with CuI and [Cu(MeCN)(4)][PF6]: Benzimidazole Formation vs. Cu Oxidation
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Reactivity of 2,2 '-Bis(2N-(1,1 ',3,3 '-tetramethyl-guanidino))diphenylene-amine with CuI and [Cu(MeCN)(4)][PF6]: Benzimidazole Formation vs. Cu Oxidation

机译:2,2'-双(2N-(1,1',3,3'-四甲基-胍基))二亚苯基胺与CuI和[Cu(MeCN)(4)] [PF6]的反应:苯并咪唑的形成铜氧化

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摘要

The reaction of 2,2'-Bis(2N-(1,1',3,3'-tetramethyl-guanidino))diphenylene-amine (TMG(2)PA) (1) with CuI in MeCN results in the formation of [Cu-II(TMG(2)PA(amid))I] (2) indicating that Cu-I is the target of an oxidative attack of the N-H proton of the ligand which itself is converted to Molecular hydrogen. In contrast, if [Cu(MeCN)(4)][PF6] is used as the Cu-I Source, [Cu-2(I)(TMGbenz)(2)][PF6]2 (3) is obtained instead. The use of the non-coordinating counterion [PF6](-) apparently prevents Cu-I from oxidation but induces itself a cyclisation reaction within the ligand which results in the formation of a benzimidazole-guanidine ligand.
机译:2,2'-双(2N-(1,1',3,3'-四甲基-胍基))二亚苯基-胺(TMG(2)PA)(1)与CuI在MeCN中的反应导致形成[Cu-II(TMG(2)PA(酰胺))I](2)表示Cu-I是配体的NH质子本身转化为分子氢的NH质子的氧化攻击的目标。相反,如果将[Cu(MeCN)(4)] [PF6]用作Cu-I源,则获得了[Cu-2(I)(TMGbenz)(2)] [PF6] 2(3)。非配位抗衡离子[PF6](-)的使用显然可以防止Cu-1氧化,但会在配体中引起环化反应,从而导致苯并咪唑-胍配体的形成。

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