Ligand-Constraint-Induced Peroxide Activation for Electrophilic Reactivity
| Autor: | Gopalan Rajaraman, Anirban Chandra, Kallol Ray, Inés Monte-Pérez, Mursaleem Ansari, Subrata Kundu |
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| Rok vydání: | 2021 |
| Předmět: |
Metal‐Peroxide Reactivity
Reaction mechanism electrophilic reactions Stereochemistry Reactive intermediate C−H bond oxidations 010402 general chemistry 01 natural sciences Peroxide Catalysis Stannoxane chemistry.chemical_compound Nucleophile phenol oxidations Reactivity (chemistry) Research Articles μ-1 2-peroxo dicobalt(III) 010405 organic chemistry Chemistry Ligand ��-1 2-peroxo dicobalt(III) General Chemistry General Medicine 0104 chemical sciences C���H bond oxidations 540 Chemie und zugeordnete Wissenschaften Electrophile ddc:540 reaction mechanism Research Article |
| Zdroj: | Angewandte Chemie (International Ed. in English) |
| DOI: | 10.18452/24074 |
| Popis: | 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 Sn6O6 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 Sn6O6 core, represents a new domain for metal−peroxide reactivity. An end‐on μ‐1,2‐peroxodicobalt(III) complex 1 involving a non‐heme ligand system, L1, supported on a Sn6O6 stannoxane core has been found to be a reactive electrophile that is capable of initiating hydrogen atom and oxygen atom transfer reactions. The electrophilicity of 1 is attributed to the constraints provided by the Sn6O6 core and represents a new domain for metal−peroxo reactivity. |
| Databáze: | OpenAIRE |
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