Modeling C-H Abstraction Reactivity of Nonheme Fe(IV)O Oxidants with Alkanes: What Role Do Counter Ions Play?

被引：67

作者：

Janardanan, Deepa ^{[1
]}

Usharani, Dandamudi ^{[1
]}

Chen, Hui ^{[1
]}

Shaik, Sason ^{[1
]}

机构：

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

来源：

JOURNAL OF PHYSICAL CHEMISTRY LETTERS | 2011年 / 2卷 / 20期

基金：

以色列科学基金会;

关键词：

DENSITY-FUNCTIONAL THERMOCHEMISTRY; EXCHANGE-ENHANCED REACTIVITY; BOND ACTIVATION; 2-STATE REACTIVITY; IRON(IV)-OXO COMPLEXES; OXOIRON(IV) COMPLEX; HYDROXYLATION; EPOXIDATION; ENERGIES; LIGANDS;

D O I：

10.1021/jz201224x

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

It is shown that the addition of CIO4- counterions to [N4PyFeO](2+) enables us to avoid the anomalies associated with the self-interaction error in DFT and to describe for the first time the entire trajectories for alkane hydroxylation and desaturation by this potent oxidant. The predicted reactivity trends for cyclohexadiene and cyclohexane reproduce the experimentally observed product selectivity and relative ease of oxidation. Furthermore, the advent of this well-behaved oxidant enables us to derive generalizing principles: (a) orbital selection rules that predict transition state structures and (b) the exchange-enhanced reactivity (EER) principle that predicts the dominance of the high-spin state during the entire oxidation process. It is shown that the orbital selection rules and EER principle are general descriptors of the reactivity of metal-oxo systems and appear to be fundamental principles of chemistry.

引用

页码：2610 / 2617

页数：8

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