| Quesne, Matthew, Senthilnathan, D., Singh, D., Kumar, D., Maldivi, P., Sorokin, A. and De Visser, S. P 2016. Origin of the enhanced reactivity of μ-nitrido-bridged diiron (IV)-oxo porphyrinoid complexes over cytochrome P450 Compound I. ACS Catalysis 6 (4) , pp. 2230-2243. 10.1021/acscatal.5b02720 |
Abstract
µ-Nitrido bridged diiron porphyrins and phthalocyanines are known to be efficient oxidants that are able to oxidize some of the strongest C–H bonds in nature, such as the one in methane. The origin of their catalytic efficiency is poorly understood and, in order to gain insight into the structural and electronic features of this chemical system, we performed a detailed and systematic study into their chemical properties and reactivities using density functional theory. Our work shows that µ-nitrido bridged diiron porphyrins and phthalocyanines are highly active catalytic oxidants, which react with methane with very low reaction barriers and a rate determining hydrogen atom abstraction step. Furthermore, the µ-nitrido bridged diiron porphyrin and phthalocyanine complexes react with a free energy of activation that is more than 10 kcal mol–1 lower in energy than, for instance, that is found for cytochrome P450 Compound I, which is known to be one of the most efficient C–H hydroxylating agents in Nature. We have analyzed the electronic configuration of reactants and transition states in detail and have identified the key properties of the oxidants
| Item Type: | Article |
|---|---|
| Date Type: | Publication |
| Status: | Published |
| Schools: | Chemistry |
| Subjects: | Q Science > QD Chemistry |
| Publisher: | American Chemical Society |
| ISSN: | 2155-5435 |
| Date of Acceptance: | 11 January 2016 |
| Last Modified: | 08 Jul 2019 10:21 |
| URI: | https://orca.cardiff.ac.uk/id/eprint/88667 |
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