Influence of Ligand Architecture on Oxidation Reactions by High‐Valent Nonheme Manganese Oxo Complexes Using Water as a Source of Oxygen1. Issue 7 (29th December 2014)

• Record Type: Journal Article
• Authors: Barman, Prasenjit; Vardhaman, Anil Kumar; Martin, Bodo; Wörner, Svenja J.; Sastri, Chivukula V.; Comba, Peter
• Is Part Of: Angewandte Chemie international edition. Volume 54:Issue 7(2015)
• Page Start: 2095
• Page End: 2099
• Publication Date: 2014-12-29
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201409476
• Languages: English
• ISSNs: 1433-7851

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>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 (L¹) is significantly more reactive than the other (L²), while in the corresponding Fe^IVO based oxidation reactions the L²‐based system was previously found to be more reactive than the L¹‐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 (σ versus π) and concomitant steric effects.</p> </abstract>