A Mechanistic Study on the Reaction of Non‐Heme Diiron(III)‐Peroxido Complexes with Benzoyl Chloride. Issue 39 (28th September 2021)

• Record Type: Journal Article
• Authors: Lerch, Markus; Achazi, Andreas J.; Mollenhauer, Doreen; Becker, Jonathan; Schindler, Siegfried
• Is Part Of: European journal of inorganic chemistry. Issue 39(2021)
• Page Start: 4122
• Page End: 4132
• Publication Date: 2021-09-28
• Subjects: Iron -- Kinetics -- Reaction mechanisms -- Substituent effects -- Time-resolved spectroscopy; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.202100711
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract: Dinuclear iron peroxido complexes are important intermediates for selective oxidation reactions. A detailed kinetic study of the reaction of benzoyl chloride (BzCl) with a dinuclear iron non‐heme cis end‐on peroxido complex with the ligand EtHPTB ( N, N, N ′, N ′‐tetrakis[( N ‐ethyl‐2‐benzimidazolyl)methyl]‐2‐hydroxy‐1, 3‐diamino‐propane) had been performed. The starting complex, the iron peroxido complex, can be obtained either by reaction of the iron(II) complex with O2 or instead, applying the corresponding iron(III) complex together with hydrogen peroxide. Using low temperature stopped‐flow measurements allowed to obtain activation parameters and in combination with a Hammet plot it was possible to postulate a mechanism for the formation of a perbenzoate complex prior to its decomposition. Furthermore, the direct reaction of the dinuclear iron(III) EtHPTB complex with peracetic acid was analyzed. Additionally, in comparison a mononuclear non‐heme iron complex with the ligand bztpen ( N ‐benzyl‐ N, N′, N′ ‐tris(2‐pyridylmethyl)ethane‐1, 2‐diamine) was investigated as well. Abstract : A rapid reaction between a dinuclear iron(III)peroxido complex and benzoyl chloride was observed in methanol. Time‐resolved UV‐vis spectra at low temperatures showed a clean decay of the peroxido complex with simultaneous formation of an intermediate that we assign as an iron(IV)oxido/benzoato radical species.