Electronic and ligand properties of annelated normal and abnormal (mesoionic) N-heterocyclic carbenes: a theoretical study.
Electronic and ligand properties of annelated normal and abnormal (mesoionic) N-heterocyclic carbenes: a theoretical study.
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正常和异常（介离子）N-杂环卡宾的电子和配体特性：理论研究。
DOI：
10.1021/jo402057g
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发表时间：
2013
期刊：
影响因子：
--
通讯作者：
Rian D. Dewhurst
中科院分区：
文献类型：
--
作者：
A. K. Phukan;A. Guha;S. Sarmah;Rian D. Dewhurst
用量子化学方法研究了环化和羰基化对N-杂环卡宾（NHC）电子性质和配位性质的影响。这些NHC的热力学和动力学稳定性已被评估的基础上，他们的单重态-三重态和HOMO-LUMO间隙分别。已经发现，缩合和羰基化都会降低NHC的稳定性。与未稠合的卡宾相比，稠合的和羰基化的卡宾是较弱的σ供体，但较好的π受体。然而，羰基化的效果是更明显的比annealing对增加的π酸性的NHC。这些卡宾的反应性进行了讨论的亲核性和亲电性指数。相应的卡宾-膦烯加合物的相对氧化还原电位和（31）P NMR化学位移的计算值与NHC的π酸性有很好的相关性。
The effect of annelation and carbonylation on the electronic and ligating properties of N-heterocyclic carbenes (NHCs) has been studied quantum chemically. The thermodynamic and kinetic stability of these NHCs have been assessed on the basis of their singlet-triplet and HOMO-LUMO gaps respectively. Both annelation and carbonylation have been found to decrease the stability of NHCs. Compared to nonannelated carbenes, annelated and carbonylated carbenes are found to be weaker σ donors but better π acceptors. However, the effect of carbonylation is more pronounced than annelation toward increasing the π acidity of the NHCs. The reactivity of these carbenes has been discussed in terms of nucleophilicity and electrophilicity indices. The calculated values of the relative redox potential and (31)P NMR chemical shifts of corresponding carbene-phosphinidene adducts have been found to correlate well with the π acidity of the NHCs.
影响因子：
16.6
作者：
Martin, David;Lassauque, Nicolas;Donnadieu, Bruno;Bertrand, Guy
通讯作者：
Bertrand, Guy
影响因子：
16.6
作者：
Back, Olivier;Henry-Ellinger, Martin;Bertrand, Guy
通讯作者：
Bertrand, Guy