Direct Synthesis of a Copper(II) N-Heterocyclic Carbene Complex in Air,Organometallics

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Direct Synthesis of a Copper(II) N-Heterocyclic Carbene Complex in Air
Organometallics ( IF 2.5 ) Pub Date : 2017-08-29 00:00:00 , DOI: 10.1021/acs.organomet.7b00489
Daniel J. O’Hearn ₁ , Robert D. Singer ₁

Affiliation

Copper N-heterocyclic carbene complexes (Cu-NHCs) are prevalent in the literature, and their stability and catalytic activity have been well characterized and established. In an overwhelming majority of the reported examples, copper is present as Cu(I), owing to the favorable soft–soft interaction. In contrast, there are very few reports of Cu-NHCs containing Cu(II). This can be explained by the unfavorable intermediate/hard–soft interaction between carbon and Cu(II). The syntheses of examples reported thus far require the exclusion of air and moisture and involve the use of NHC transfer reagents or the use of free NHCs. This results in tedious, multistep procedures, making their preparation more time consuming and costly. Herein we report the synthesis and characterization of two air- and moisture-stable Cu(II)-NHC complexes by direct combination of 1,3-bis(pyridin-2-ylmethyl)-1H-imidazolium chloride with copper(II) hexafluorosilicate. Analysis by single-crystal X-ray diffraction revealed that the species could be isolated in both distorted-octahedral and distorted-square-pyramidal geometries.

中文翻译：

空气中直接合成铜（II）N-杂环碳配合物

N-杂环卡宾铜配合物（Cu-NHCs）在文献中很普遍，其稳定性和催化活性已得到很好的表征和证实。在绝大多数报道的例子中，由于有利的软-软相互作用，铜以Cu（I）的形式存在。相比之下，关于含Cu（II）的Cu-NHC的报道很少。这可以用碳和Cu（II）之间不利的中间/软硬相互作用来解释。迄今为止报道的实施例的合成需要排除空气和湿气，并且涉及使用NHC转移试剂或使用游离NHC。这导致繁琐的多步骤程序，使其准备工作更加耗时且成本更高。H-咪唑氯化物与六氟硅酸铜（II）。通过单晶X射线衍射分析表明，该物种可以在扭曲的八面体和扭曲的方金字塔形几何形状中分离。

更新日期：2017-08-29

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