Ligand-Constraint-Induced Peroxide Activation for Electrophilic Reactivity

Overview

Journal Angew Chem Int Ed Engl

Specialty Chemistry

Date 2021 Apr 12

PMID 33843113

Citations 1

Authors

Anirban Chandra

Mursaleem Ansari

Ines Monte-Perez

Subrata Kundu

Gopalan Rajaraman

Kallol Ray

Affiliations

Soon will be listed here.

Abstract

μ-1,2-peroxo-bridged diiron(III) intermediates P are proposed as reactive intermediates in various biological oxidation reactions. In sMMO, P acts as an electrophile, and performs hydrogen atom and oxygen atom transfers to electron-rich substrates. In cyanobacterial ADO, however, P is postulated to react by nucleophilic attack on electrophilic carbon atoms. In biomimetic studies, the ability of μ-1,2-peroxo-bridged dimetal complexes of Fe, Co, Ni and Cu to act as nucleophiles that effect deformylation of aldehydes is documented. By performing reactivity and theoretical studies on an end-on μ-1,2-peroxodicobalt(III) complex 1 involving a non-heme ligand system, L1, supported on a Sn O stannoxane core, we now show that a peroxo-bridged dimetal complex can also be a reactive electrophile. The observed electrophilic chemistry, which is induced by the constraints provided by the Sn O core, represents a new domain for metal-peroxide reactivity.

Citing Articles

Ligand-Constraint-Induced Peroxide Activation for Electrophilic Reactivity.

Chandra A, Ansari M, Monte-Perez I, Kundu S, Rajaraman G, Ray K Angew Chem Int Ed Engl. 2021; 60(27):14954-14959.

PMID: 33843113 PMC: 8252416. DOI: 10.1002/anie.202100438.

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