The Origins of Dramatic Axial Ligand Effects: Closed-Shell MnVO Complexes Use Exchange-Enhanced Open-Shell States to Mediate Efficient H Abstraction Reactions

被引：40
作者：
Janardanan, Deepa [1 ,2 ]
Usharani, Dandamudi [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
来源：
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2012年 / 51卷 / 18期
关键词：
density functional calculations; exchange-enhanced reactivity; high-valent Mn-oxo; hydrogen atom abstraction; BOND ACTIVATION; SPIN-STATE; ATOM TRANSFER; REACTIVITY; TRANSITION; PORPHYRINS; CATION; MANGANESE(III); DECOMPOSITION; HYDROXYLATION;
D O I：
10.1002/anie.201200689
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
Spin-state effects: In [(Cz)Mn VO] complexes, even with singlet closed-shell ground states, the reactive state is the open-shell triplet B state (S B=1) that has a high oxyl radical character and a transition state (TS) stabilized by exchange-enhanced reactivity (EER; see picture). The dramatic axial ligand effect originates in the EER of this state. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
引用
收藏
页码：4421 / 4425
页数：5
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