Global and local reactivity indices for electrophilic/nucleophilic free radicals
Global and local reactivity indices for electrophilic/nucleophilic free radicals
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DOI：
10.1039/c3ob40337h
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发表时间：
2013-01-01
影响因子：
3.2
通讯作者：
Perez, Patricia
中科院分区：
文献类型：
--
作者：
Domingo, Luis R.;Perez, Patricia
提出了一组用于自由基研究的五个DFT反应性指数，即整体亲电性Ω度和亲核性N度指数、自由基Parr函数P度（k）、局部亲电性Ω度（k）和亲核性N度（k）指数.已经测试了一系列具有亲电和/或亲核活化的32个FR的全局指数。正如预期的那样，没有发现之间的相关性提出的全球亲电性Ω度和亲核性N度（k）的局部亲电性Ω度（k）和亲核性N度（k）的指数，与分析的局部亲电性Ω（k）和亲核性N-k指数的烯烃，允许的区域和化学选择性的自由基加成的FR烯烃的解释。最后，对C-C键形成沿着2-羟基丙-2-基FR 28与丙烯酸甲酯35的亲核加成的ELF键合分析证明，新的C-C键是通过两个自由基中心的C-C偶联形成的，其通过使用Parr函数适当地表征。
A set of five DFT reactivity indices, namely, the global electrophilicity omega degrees and nucleophilicity N degrees indices, the radical Parr function P degrees(k), and the local electrophilicity omega degrees(k) and nucleophilicity N degrees(k) indices, for the study of free radicals (FRs) are proposed. Global indices have been tested for a series of 32 FRs having electrophilic and/or nucleophilic activations. As expected, no correlation between the proposed global electrophilicity omega degrees and global nucleophilicity N degrees has been found. Analysis of the local electrophilicity omega degrees(k) and nucleophilicity N degrees(k) indices for FRs, together with analysis of the local electrophilicity omega(k) and nucleophilicity N-k indices for alkenes, allows for an explanation of the regio- and chemoselectivity in radical additions of FRs to alkenes. Finally, an ELF bonding analysis for the C-C bond formation along the nucleophilic addition of 2-hydroxyprop-2-yl FR 28 to methyl acrylate 35 evidences that the new C-C bond is formed by C-to-C coupling of two radical centres, which are properly characterized through the use of the Parr functions.