Mechanistic Insights into Unusual Reactions by High -Valent Iron Intermediates
| dc.contributor.author | Sastri, Chivukula V. | |
| dc.date.accessioned | 2015-09-22T09:57:37Z | |
| dc.date.accessioned | 2023-10-19T12:15:25Z | |
| dc.date.available | 2015-09-22T09:57:37Z | |
| dc.date.available | 2023-10-19T12:15:25Z | |
| dc.date.issued | 2013 | |
| dc.description | Supervisor: Chivukula V. Sastri | en_US |
| dc.description.abstract | High-valent non-heme iron(III)-hydroperoxo and iron(IV)-oxo units are proposed as key oxidizing intermediates in many biological iron dependent oxygenases. The oxidant, iron(IV)-oxo species were proposed as active oxidant in several catalytic cycles. In recent years, emphasis on the evaluation of the kinetic and mechanistic insights into the reactivity of iron(IV)-oxo, iron(III)- hydroperoxo and other high-valent isolabal intermediates have increased. In the present work, the reactivity studies towards halide oxidation, Soxidation, C-H activation with high-valent iron(III)-hydroperoxo, iron(IV)-oxo and iron(IV)-imido species supported by penta-dentate ligands have been evaluated. These reactivity studies provide remarkable insights into the mechanistic pathway of these intermediates. Iron(III)-hydroproxo and iron(IV)-oxo complexes were compared in halide oxidation and observed that iron(III)-hydroproxo were efficient oxidizing species. In comparison of Iron(IV)-oxo and iron(IV)-imido complexes towards Soxidation and C-H activation, a conflicting results were observed. For Soxidation reactions, iron(IV)-imido complexes were a better oxidants as compared to iron(IV)-oxo. On the contrary, for C-H activation a complete reversal of the reactivity was observed where in iron(IV)-oxo species were more reaction than iron(IV)-imido complexes. Finally, the reactivity of iron(IV)-oxo complexes were evaluated for the oxidation of one of the most difficult pollutant (dibenzothiophene) and its thermodynamic parameters were evaluated.. | en_US |
| dc.identifier.other | ROLL NO. 08612223 | |
| dc.identifier.uri | https://gyan.iitg.ac.in/handle/123456789/484 | |
| dc.language.iso | en | en_US |
| dc.relation.ispartofseries | TH-1264; | |
| dc.subject | CHEMISTRY | en_US |
| dc.title | Mechanistic Insights into Unusual Reactions by High -Valent Iron Intermediates | en_US |
| dc.type | Thesis | en_US |