School of Chemistry, University of New South Wales, Sydney 2052, Australia.
Dalton Trans. 2019 Mar 12;48(11):3576-3582. doi: 10.1039/c8dt04858d.
This work demonstrates that simple copper-bipyridine compounds and atmospheric CO2 react to produce useful/complex materials under appropriate conditions. Starting from a distorted square planar copper(ii) complex, [(tbubpy)CuCl2](tbubpy = 4-tert-butyl-2-(4-tert-butylpyridin-2-yl)pyridine), an air-sensitive, copper(i) complex, [(tbubpy)2CuI][BF4], which exhibits a distorted tetrahedral geometry, was synthesized and characterized. Reactions of [(tbubpy)2CuI][BF4] with CO2 inside a sealed tube and with air were carried out over a week and three weeks, respectively. A new tricopper(ii)-carbonato cluster, [{(tbubpy)2Cu}3(μ-CO3)][PF6]4, was isolated with three distorted octahedral copper(ii) centres bound by a carbonate-bridge formed from atmospheric CO2. NMR and UV-Vis spectroscopic analyses coupled with previous reports point to a multi-step process in the formation of a trinuclear CuII-carbonato cluster that includes the probable involvement of μ-hydroxo-bridged dicopper(ii) type intermediates.
这项工作表明，在适当的条件下，简单的铜-联吡啶化合物和大气中的 CO2 反应可以产生有用/复杂的材料。从扭曲的正方形平面铜（ii）配合物[（tbubpy）CuCl2]（tbubpy = 4-叔丁基-2-（4-叔丁基-2-吡啶基）吡啶）开始，合成并表征了一种对空气敏感的铜（i）配合物[（tbubpy）2CuI][BF4]，其具有扭曲的四面体形几何形状。在密封管内和空气中，分别对[（tbubpy）2CuI][BF4]与 CO2 的反应进行了一周和三周的反应。通过使用大气 CO2 形成的碳酸盐桥，分离出了一种新型三铜（ii）-碳酸盐簇[（（tbubpy）2Cu）3（μ-CO3）][PF6]4，其中三个扭曲的八面体铜（ii）中心通过碳酸盐桥连接。NMR 和 UV-Vis 光谱分析以及以前的报告表明，形成三核 CuII-碳酸盐簇的过程是多步的，包括可能涉及μ-羟基桥联二铜（ii）型中间体。
