Computational and Experimental Insights into a Ferric Cumylperoxido Species Stabilized in a Bispidine Scaffold
Iron‐containing alkylperoxido species are mostly unstable, although these are important reactive intermediates found in metalloenzymes. Noncovalent forces in enzymatic systems contribute to their stability and reactivity. Different mechanistic approaches such as OO bond cleavage and FeO bond cleavage are established pathways of their reactivity. However, with a thorough computational study combined with experiments, we have discovered a different approach wherein we report a putative superoxido species orchestrating the unique mechanism. Herein, we discuss the generation and reactivity of an iron(III)‐cumylperoxido intermediate towards sulfoxidation and aldehyde deformylation, supported and corroborated by an in‐depth computational analysis.
Authors
- Gourab Mukherjee (ORCID: https://orcid.org/0000-0002-7150-5570)
- Peter Comba (ORCID: https://orcid.org/0000-0001-7796-3532)
- Gunasekaran Velmurugan (ORCID: https://orcid.org/0000-0003-3244-2690)
- Umesh Kumar Bagha (ORCID: https://orcid.org/0000-0003-1194-6208)
- Chivukula V. Sastri (ORCID: https://orcid.org/0000-0003-0477-7741)
Institutions
- Indian Institute of Technology Guwahati (IN)
- Heidelberg University (DE)
- Indian Institute of Chemical Technology (IN)
Publication Details
- Journal
- Zeitschrift für anorganische und allgemeine Chemie
- Published
- 2025-10-13
- DOI
- https://doi.org/10.1002/zaac.202500189
- Primary Topic
- Metal-Catalyzed Oxygenation Mechanisms
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- Department of Science and Technology, Ministry of Science and Technology, India
- Deutsche Forschungsgemeinschaft
- Bundesministerium für Bildung und Forschung
- Max-Planck-Gesellschaft
- Ministry of Education, India
- Indian Institute of Technology Guwahati
- Science and Engineering Research Board