Mechanistic insights into amphoteric reactivity of an iron-bispidine complex

• Verfasst von: Mukherjee, Gourab [VerfasserIn]
• Verfasst von: Velmurugan, Gunasekaran [VerfasserIn]
• Verfasst von: Kerscher, Marion [VerfasserIn]
• Verfasst von: Kumar Satpathy, Jagnyesh [VerfasserIn]
• Verfasst von: Sastri, Chivukula V. [VerfasserIn]
• Verfasst von: Comba, Peter [VerfasserIn]
• Titel: Mechanistic insights into amphoteric reactivity of an iron-bispidine complex
• Verf.angabe: Gourab Mukherjee, Gunasekaran Velmurugan, Marion Kerscher, Jagnyesh Kumar Satpathy, Chivukula V. Sastri, and Peter Comba
• E-Jahr: 2024
• Jahr: January 11, 2024
• Umfang: 7 S.
• Fussnoten: Erstmals veröffentlicht: 09 November 2023 ; Gesehen am 19.01.2024
• Titel Quelle: Enthalten in: Chemistry - a European journal
• Ort Quelle: Weinheim : Wiley-VCH, 1995
• Jahr Quelle: 2024
• Band/Heft Quelle: 30(2024), 3 vom: Jan., Artikel-ID e202303127, Seite 1-7
• ISSN Quelle: 1521-3765
• DOI: doi:10.1002/chem.202303127
• Datenträger: Online-Ressource
• Sprache: eng
• Sach-SW: aldehyde deformylation
• Sach-SW: DFT
• Sach-SW: metal-oxygen adducts
• Sach-SW: reaction mechanisms
• Sach-SW: sulfoxidation
• K10plus-PPN: 1878486659

Abstract

The reactivity of FeIII-alkylperoxido complexes has remained a riddle to inorganic chemists owing to their thermal instability and impotency towards organic substrates. These iron-oxygen adducts have been known as sluggish oxidants towards oxidative electrophilic and nucleophilic reactions. Herein, we report the synthesis and spectroscopic characterization of a relatively stable mononuclear high-spin FeIII-alkylperoxido complex supported by an engineered bispidine framework. Against the notion, this FeIII-alkylperoxido complex serves as a rare example of versatile reactivity in both electrophilic and nucleophilic reactions. Detailed mechanistic studies and computational calculations reveal a novel reaction mechanism, where a putative superoxido intermediate orchestrates the amphoteric property of the oxidant. The design of the backbone is pivotal to convey stability and reactivity to alkylperoxido and superoxido intermediates. Contrary to the well-known O−O bond cleavage that generates an FeIV-oxido species, the FeIII-alkylperoxido complex reported here undergoes O−C bond scission to generate a superoxido moiety that is responsible for the amphiphilic reactivity.