A tutorial for understanding chemical reactivity through the valence bond approach

被引：50

作者：

Usharani, Dandamudi ^{[1
,2
]}

Lai, Wenzhen ^{[3
]}

Li, Chunsen ^{[4
,5
]}

Chen, Hui ^{[6
]}

Danovich, David ^{[1
,2
]}

Shaik, Sason ^{[1
,2
]}

机构：

[1] Hebrew Univ Jerusalem, Inst Chem, IL-91904 Jerusalem, Israel

[2] Hebrew Univ Jerusalem, Lise Meitner Minerva Ctr Computat Quantum Chem, IL-91904 Jerusalem, Israel

[3] Renmin Univ China, Dept Chem, Beijing 100872, Peoples R China

[4] Chinese Acad Sci, Fujian Inst Res Struct Matter, State Key Lab Struct Chem, Fuzhou 350002, Fujian, Peoples R China

[5] Fujian Prov Key Lab Theoret & Computat Chem, Xiamen 361005, Fujian, Peoples R China

[6] Chinese Acad Sci, Inst Chem, CAS Key Lab Photochem, BNLMS, Beijing 100190, Peoples R China

来源：

CHEMICAL SOCIETY REVIEWS | 2014年 / 43卷 / 14期

关键词：

HYDROGEN-ATOM TRANSFER; COUPLED ELECTRON-TRANSFER; CARBON-CENTERED RADICALS; ABSTRACTION REACTIONS; SN2; REACTIVITY; CYTOCHROME-P450; HYDROXYLATION; PATTERNS; DIAGRAM; ACTIVATION;

D O I：

10.1039/c4cs00043a

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

This is a tutorial on the usage of valence bond (VB) diagrams for understanding chemical reactivity in general, and hydrogen atom transfer (HAT) reactivity in particular. The tutorial instructs the reader how to construct the VB diagrams and how to estimate HAT barriers from raw data, starting with the simplest reaction H + H-2 and going all the way to HAT in the enzyme cytochrome P450. Other reactions are treated as well, and some unifying principles are outlined. The tutorial projects the unity of reactivity treatments, following Coulson's dictum "give me insight, not numbers'', albeit with its modern twist: giving numbers and insight.

引用

页码：4968 / 4988

页数：21

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