Four-Coordinate Copper Halonitrosyl {CuNO}10 Complexes
Four-Coordinate Copper Halonitrosyl {CuNO}10 Complexes
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DOI：
10.1002/anie.201904732
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发表时间：
2019-07-22
影响因子：
16.6
通讯作者：
Zhang, Shiyu
中科院分区：
文献类型：
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作者：
Bower, Jamey K.;Sokolov, Alexander Yu;Zhang, Shiyu
虽然亚硝基铜配合物与许多生物系统有关，但可分离的例子仍然有限。在这篇报告中，我们证明了具有{CuNO}（10）电子构型的[Cl3CuNO]（-）可以通过亚硝酸盐还原在二氯化铜(I)阴离子上或通过在三氯化铜（II）前驱体上添加一氧化氮来生成。以类似物的方式合成了溴的类似物[Br3CuNO](-)，并用x射线衍射和各种光谱方法对两种卤代硝基铜配合物进行了表征。实验数据和多参考（CASSCF/NEVPT2）计算为Cu-II-NO的存在提供了强有力的证据。基态。[Cl3CuNO]（-）和[Br3CuNO]（-）释放和重新捕获NO。对各种生物亲核试剂，如胺、醇和硫醇，均表现出亚硝化反应。
While copper nitrosyl complexes are implicated in numerous biological systems, isolable examples remain limited. In this report, we show that [Cl3CuNO](-), with a {CuNO}(10) electron configuration, can be generated by nitrite reduction at a copper(I) dichloride anion or by nitric oxide addition to a copper(II) trichloride precursor. The bromide analogue, [Br3CuNO](-) was synthesized analogously, and both copper halonitrosyl complexes were characterized by X-ray diffraction and a variety of spectroscopic methods. Experimental data and multireference (CASSCF/NEVPT2) calculations provide strong evidence for a Cu-II-NO. ground state. Both [Cl3CuNO](-) and [Br3CuNO](-) release and recapture NO. reversibly, and exhibit nitrosative reactivities toward a wide range of biological nucleophiles, such as amines, alcohols, and thiols.