Cu(II)-alkyl chlorocomplexes: stable compounds or transients? DFT prediction of their structure and EPR parameters.
Cu(II)-alkyl chlorocomplexes: stable compounds or transients? DFT prediction of their structure and EPR parameters.
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Cu(II)-烷基氯络合物：稳定化合物还是瞬态化合物？
DOI：
10.1021/jp202314h
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发表时间：
2011
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影响因子：
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通讯作者：
G. Zhidomirov
中科院分区：
文献类型：
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作者：
E. Golubeva;O. Gromov;G. Zhidomirov
用密度泛函理论（DFT）研究了具有弱Cu-C键的有机铜酸酯（II）的结构和反应活性。结果发现，计算的模型化合物RCu（II）Cl（2（-））的主g-张量值是类似的实验发现的值为有机铜产品的四氯铜酸季铵的光解。计算证实，大多数的有机铜酸盐（II）可以在环境条件下是稳定的，和短的寿命的有机铜酸盐（II）在溶液中或软基质是由于它们的高反应性在各种双分子过程中，这些速率可能是接近的扩散控制反应的速率。电荷，自旋密度，和d-轨道人口的铜原子在他们是典型的二价铜配合物。有机氯铜酸盐（II）的自然键轨道分析证实了铜和碳原子之间形成极性σ-键。
DFT calculations were used for studying the structure and reactivity of organocuprates(II) usually considered as intermediates with very weak Cu-C bond. It was found that calculated principal g-tensor values of model compounds RCu(II)Cl(2(-)) are similar to the experimentally found values for organocopper product of photolysis of quaternary ammonium tetrachlorocuprates. The calculations confirm that the most of organocuprates(II) could be stable at ambient conditions, and short lifetimes of organocuprates(II) in solutions or soft matrices are caused by their high reactivity in various bimolecular processes; the rate of those may be close to the rate of diffusion controlled reactions. The charges, spin densities, and d-orbital populations of the Cu atom in them are typical for bivalent copper complexes. Natural bond orbital analysis of organochlorocuprates(II) confirms the formation of polar σ-bond between copper and carbon atoms.
影响因子：
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作者：
R. Santo;Riichi Miyamoto;R. Tanaka;T. Nishioka;Kazunobu Sato;K. Toyota;M. Obata;S. Yano;I. Kinoshita;A. Ichimura;T. Takui
通讯作者：
R. Santo;Riichi Miyamoto;R. Tanaka;T. Nishioka;Kazunobu Sato;K. Toyota;M. Obata;S. Yano;I. Kinoshita;A. Ichimura;T. Takui
影响因子：
15
作者：
Maeda, H;Ishikawa, Y;Furuta, H
通讯作者：
Furuta, H
Masahiro Yamanaka：“有机铜（I）和有机铜（III）物种的结构和反应性的理论研究”计算化学杂志。
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