On the oxidation of alkyl and aryl sulfides by [(Me(3)TACN)(MnO)-O-V(OH)(2)](+): A density functional study
Density functional theory suggests that the formal 2-electron oxidation of sulfides, RR′S, to sulfoxides, RR2′ S {double bond, long} O by the model MnV{double bond, long}O catalyst, [(TACN)MnV O(OH)2]+, proceeds in two quite distinct 1-electron steps. Transfer of the first electron is barrierless an...
| Main Authors: | , , , , |
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| Format: | Journal article |
| Language: | English |
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2008
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| _version_ | 1826288597195554816 |
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| author | Anastasi, A Walton, P Smith, J Sameera, W McGrady, J |
| author_facet | Anastasi, A Walton, P Smith, J Sameera, W McGrady, J |
| author_sort | Anastasi, A |
| collection | OXFORD |
| description | Density functional theory suggests that the formal 2-electron oxidation of sulfides, RR′S, to sulfoxides, RR2′ S {double bond, long} O by the model MnV{double bond, long}O catalyst, [(TACN)MnV O(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 MnIV centre via a covalent μ-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. © 2007 Elsevier B.V. All rights reserved. |
| first_indexed | 2024-03-07T02:16:04Z |
| format | Journal article |
| id | oxford-uuid:a248f32c-d045-41d2-8025-386517709d62 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T02:16:04Z |
| publishDate | 2008 |
| record_format | dspace |
| spelling | oxford-uuid:a248f32c-d045-41d2-8025-386517709d622022-03-27T02:19:09ZOn the oxidation of alkyl and aryl sulfides by [(Me(3)TACN)(MnO)-O-V(OH)(2)](+): A density functional studyJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:a248f32c-d045-41d2-8025-386517709d62EnglishSymplectic Elements at Oxford2008Anastasi, AWalton, PSmith, JSameera, WMcGrady, JDensity functional theory suggests that the formal 2-electron oxidation of sulfides, RR′S, to sulfoxides, RR2′ S {double bond, long} O by the model MnV{double bond, long}O catalyst, [(TACN)MnV O(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 MnIV centre via a covalent μ-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. © 2007 Elsevier B.V. All rights reserved. |
| spellingShingle | Anastasi, A Walton, P Smith, J Sameera, W McGrady, J On the oxidation of alkyl and aryl sulfides by [(Me(3)TACN)(MnO)-O-V(OH)(2)](+): A density functional study |
| title | On the oxidation of alkyl and aryl sulfides by [(Me(3)TACN)(MnO)-O-V(OH)(2)](+): A density functional study |
| title_full | On the oxidation of alkyl and aryl sulfides by [(Me(3)TACN)(MnO)-O-V(OH)(2)](+): A density functional study |
| title_fullStr | On the oxidation of alkyl and aryl sulfides by [(Me(3)TACN)(MnO)-O-V(OH)(2)](+): A density functional study |
| title_full_unstemmed | On the oxidation of alkyl and aryl sulfides by [(Me(3)TACN)(MnO)-O-V(OH)(2)](+): A density functional study |
| title_short | On the oxidation of alkyl and aryl sulfides by [(Me(3)TACN)(MnO)-O-V(OH)(2)](+): A density functional study |
| title_sort | on the oxidation of alkyl and aryl sulfides by me 3 tacn mno o v oh 2 a density functional study |
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