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

Anastasi, A. E., Walton, P. H., Smith, J. R. L., Sameera, W. M. C. and McGrady, J. E. (2008) On the oxidation of alkyl and aryl sulfides by [(Me(3)TACN)(MnO)-O-V(OH)(2)](+): A density functional study. Inorganica Chimica Acta, 361(4), pp. 1079-1086. (doi: 10.1016/j.ica.2007.08.009)

Abstract

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. .

• Item Type: Articles
• Keywords: CATALYST CATION COMPLEX-CARBOXYLIC-ACID DENSITY Density functional theory ELECTRON ELECTRON-TRANSFER ELECTRONIC-STRUCTURE high-valent manganese HYDROGEN-PEROXIDE MANGANESE 1,4,7-TRIMETHYL-1,4,7-TRIAZACYCLONONANE COMPLEXES MEDIATED ALKENE EPOXIDATION MIGRATION MODEL O BOND FORMATION OXIDATION OXO(SALEN)MANGANESE(V) COMPLEXES OXOMANGANESE(V) PORPHYRIN REACTIVITY-SELECTIVITY PRINCIPLE SALEN COMPLEXES STEP SUBSTITUENTS sulfide SULFOXIDES SULFUR
• Status: Published
• Refereed: Yes
• Glasgow Author(s) Enlighten ID: McGrady, Prof John
• Authors: Anastasi, A. E., Walton, P. H., Smith, J. R. L., Sameera, W. M. C., and McGrady, J. E.
• College/School: College of Science and Engineering > School of Chemistry
• Journal Name: Inorganica Chimica Acta
• ISSN: 0020-1693