Interconversion of Metallanaphthalynes and Indenylidene Complexes: A DFT Prediction
Interconversion of Metallanaphthalynes and Indenylidene Complexes: A DFT Prediction
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金属萘与茚叉配合物的相互转化：DFT 预测
DOI：
10.1021/om400537m
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发表时间：
2013-11-11
期刊：
影响因子：
2.8
通讯作者：
Zhu, Jun
中科院分区：
文献类型：
--
作者：
Fan, Jinglan;An, Ke;Zhu, Jun
金属芳族化合物引起了理论和实验化学家的极大兴趣。然而，迄今为止仅分离出两种金属萘。因此，开发新的合成方法刻不容缓。在这里，我们对金属萘和金属茚基配合物之间异构化的热力学和动力学进行了彻底的密度泛函理论（DFT）计算。系统地研究了金属中心、配体和取代基对金属双环的影响。我们的结果表明，与第三行过渡金属相比，第二行金属更倾向于形成金属茚叉而不是金属萘。此外，π-供体和π-受体配体可以分别稳定金属萘和茚基配合物。间位的空间效应也在金属萘的稳定中发挥作用。间位的给电子基团 (EDG) 和第二行过渡金属给出较低的条...
Metallaaromatics have attracted considerable interest of both theoretical and experimental chemists. However, there have been only two metallanaphthalynes isolated so far. Thus, developing new synthetic approaches is urgent. Here we present thorough density functional theory (DFT) calculations on the thermodynamics and kinetics of the isomerization between metallanaphthalynes and metal indenylidene complexes. The effects of metal centers, ligands, and substituents on the metallabicycles were examined systematically. Our results reveal that, in comparison with the third-row transition metals, the second-row metals have a tendency to form metal indenylidenes rather than metallanaphthalynes. In addition, π-donor and π-acceptor ligands can stabilize the metallanaphthalynes and indenylidene complexes, respectively. Steric effects at the meta position also play a role in the stabilization of metallanaphthalynes. Electron-donating groups (EDGs) at the meta position and second-row transition metals give lower bar...