Devi, T and Dutta, K and Deutscher, J and Mebs, S and Kuhlmann, U and Haumann, M and Cula, B and Dau, H and Hildebrandt, P and Ray, K (2023) A high-spin alkylperoxo-iron(iii) complex with cis-anionic ligands: implications for the superoxide reductase mechanism. In: Chemical Science, 15 (2). pp. 528-533.
|
PDF
che_sci_15_2_2023.pdf - Published Version Download (1MB) | Preview |
Abstract
The N3O macrocycle of the 12-TMCO ligand stabilizes a high spin (S = 5/2) FeIII(12-TMCO)(OOtBu)Cl+ (3-Cl) species in the reaction of FeII(12-TMCO)(OTf)2 (1-(OTf)2) with tert-butylhydroperoxide (tBuOOH) in the presence of tetraethylammonium chloride (NEt4Cl) in acetonitrile at �20 °C. In the absence of NEt4Cl the oxo-iron(iv) complex 2 FeIV(12-TMCO)(O)(CH3CN)2+ is formed, which can be further converted to 3-Cl by adding NEt4Cl and tBuOOH. The role of the cis-chloride ligand in the stabilization of the FeIII-OOtBu moiety can be extended to other anions including the thiolate ligand relevant to the enzyme superoxide reductase (SOR). The present study underlines the importance of subtle electronic changes and secondary interactions in the stability of the biologically relevant metal-dioxygen intermediates. It also provides some rationale for the dramatically different outcomes of the chemistry of iron(iii)peroxy intermediates formed in the catalytic cycles of SOR (Fe-O cleavage) and cytochrome P450 (O-O bond lysis) in similar N4S coordination environments. © 2024 The Royal Society of Chemistry.
| Item Type: | Journal Article |
|---|---|
| Publication: | Chemical Science |
| Publisher: | Royal Society of Chemistry |
| Additional Information: | The copyright for this article belongs to authors. |
| Keywords: | Chlorine compounds; Iron compounds, Anionic ligands; Chloride ligands; Electronic changes; High spins; Macrocycles; Secondary interactions; Superoxide reductase; Tert-butylhydroperoxide; Tetraethylammonium; Thiolate ligands, Ligands |
| Department/Centre: | Division of Chemical Sciences > Inorganic & Physical Chemistry |
| Date Deposited: | 16 Nov 2024 15:21 |
| Last Modified: | 16 Nov 2024 15:21 |
| URI: | http://eprints.iisc.ac.in/id/eprint/85313 |
Actions (login required)
 |
View Item |
