On the oxidation of alkyl and aryl sulfides by [(Me(3)TACN)(MnO)-O-V(OH)(2)](+): A density functional study

TY - JOUR

T1 - On the oxidation of alkyl and aryl sulfides by [(Me(3)TACN)(MnO)-O-V(OH)(2)](+): A density functional study

AU - Anastasi, Anna E.

AU - Walton, Paul H.

AU - Smith, John R. Lindsay

AU - Sameera, Wickramarachchi M. C.

AU - McGrady, John E.

PY - 2008/3/3

Y1 - 2008/3/3

N2 - Density functional theory suggests that the formal 2-electron oxidation of sulfides, RR'S, to sulfoxides, (RR2S)-S-'=O by the model Mn-V=O catalyst, [(TACN)(MnO)-O-V(OH)(2)](+), proceeds in two quite distinct 1-electron steps. Transfer of the first electron is barrierless and generates a sulfur radical cation, antiferromagnetically coupled to a Mn-IV centre via a covalent mu-oxo bridge. The second electron-transfer step is accompanied by migration of the oxygen atom to the sulfur centre, and is rate-determining. The absence of a barrier in the first step, where a sulfur radical is formed, means that the presence of electron-donating or withdrawing substituents on the sulfide has only a minor impact on the rate of reaction. (C) 2007 Elsevier B.V. All rights reserved.

AB - Density functional theory suggests that the formal 2-electron oxidation of sulfides, RR'S, to sulfoxides, (RR2S)-S-'=O by the model Mn-V=O catalyst, [(TACN)(MnO)-O-V(OH)(2)](+), proceeds in two quite distinct 1-electron steps. Transfer of the first electron is barrierless and generates a sulfur radical cation, antiferromagnetically coupled to a Mn-IV centre via a covalent mu-oxo bridge. The second electron-transfer step is accompanied by migration of the oxygen atom to the sulfur centre, and is rate-determining. The absence of a barrier in the first step, where a sulfur radical is formed, means that the presence of electron-donating or withdrawing substituents on the sulfide has only a minor impact on the rate of reaction. (C) 2007 Elsevier B.V. All rights reserved.

KW - density functional theory

KW - high-valent manganese

KW - sulfide

KW - oxidation

KW - COMPLEX-CARBOXYLIC-ACID

KW - MANGANESE 1,4,7-TRIMETHYL-1,4,7-TRIAZACYCLONONANE COMPLEXES

KW - REACTIVITY-SELECTIVITY PRINCIPLE

KW - MEDIATED ALKENE EPOXIDATION

KW - O BOND FORMATION

KW - HYDROGEN-PEROXIDE

KW - OXO(SALEN)MANGANESE(V) COMPLEXES

KW - OXOMANGANESE(V) PORPHYRIN

KW - SALEN COMPLEXES

KW - ELECTRONIC-STRUCTURE

UR - http://www.scopus.com/inward/record.url?scp=39049168551&partnerID=8YFLogxK

U2 - 10.1016/j.ica.2007.08.009

DO - 10.1016/j.ica.2007.08.009

M3 - Article

SN - 0020-1693

VL - 361

SP - 1079

EP - 1086

JO - INORGANICA CHIMICA ACTA

JF - INORGANICA CHIMICA ACTA

IS - 4

ER -