Influence of Ligand Architecture on Oxidation Reactions by High-Valent Nonheme Manganese Oxo Complexes Using Water as a Source of Oxygen

被引：56

作者：

Barman, Prasenjit ^{[1
]}

Vardhaman, Anil Kumar ^{[1
]}

Martin, Bodo ^{[2
,3
]}

Woerner, Svenja J. ^{[2
,3
]}

Sastri, Chivukula V. ^{[1
]}

Comba, Peter ^{[2
,3
]}

机构：

[1] Indian Inst Technol, Dept Chem, Gauhati 781039, Assam, India

[2] Heidelberg Univ, Anorgan Chem Inst, D-69120 Heidelberg, Germany

[3] Heidelberg Univ, Interdisciplinary Ctr Sci Comp IWR, D-69120 Heidelberg, Germany

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2015年 / 54卷 / 07期

关键词：

density functional calculations; isomers; manganese; oxidation; structure elucidation; H BOND ACTIVATION; ELECTRON-TRANSFER; DISSOCIATION ENERGIES; MULTISTATE REACTIVITY; BASIS-SETS; IRON(IV)-OXO; PHENOLS; IRON; SULFOXIDATION; HYDROCARBONS;

D O I：

10.1002/anie.201409476

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Mononuclear nonheme Mn-IV=O complexes with two isomers of a bispidine ligand have been synthesized and characterized by various spectroscopies and density functional theory (DFT). The Mn-IV=O complexes show reactivity in oxidation reactions (hydrogen-atom abstraction and sulfoxidation). Interestingly, one of the isomers (L-1) is significantly more reactive than the other (L-2), while in the corresponding Fe-IV=O based oxidation reactions the L-2-based system was previously found to be more reactive than the L-1-based catalyst. This inversion of reactivities is discussed on the basis of DFT and molecular mechanics (MM) model calculations, which indicate that the order of reactivities are primarily due to a switch of reaction channels (sigma versus pi) and concomitant steric effects.

引用

页码：2095 / 2099

页数：5