Cerium-Complex-Catalyzed Oxidation of Arylmethanols under Atmospheric Pressure of Dioxygen and Its Mechanism through a Side-On μ-Peroxo Dicerium(IV) Complex

Chemistry : a European Journal
Mitali PaulKazushi Mashima

Abstract

A new Ce(IV) complex [Ce{NH(CH2CH2N=CHC6H2-3,5-(tBu)2-2-O)2}(NO3)2] (1), bearing a dianionic pentadentate ligand with an N3O2 donor set, has been prepared by treating (NH4)2Ce(NO3)6 with the sodium salt of ligand L1. Complex 1 in the presence of TEMPO and 4 Å molecular sieves (MS4 A) has been found to serve as a catalyst for the oxidation of arylmethanols using dioxygen as an oxidant. We propose an oxidation mechanism based on the isolation and reactivity study of a trivalent cerium complex [Ce{NH(CH2CH2N=CHC6H2-3,5-(tBu)2-2-O)2}(NO3)(THF)] (2), its side-on μ-O2 adduct [Ce{NH(CH2CH2N=CHC6H2-3,5-(tBu)2-2-O)2}(NO3)]2(μ-η(2):η(2)-O2) (3), and the hydroxo-bridged Ce(IV) complex [Ce{NH(CH2CH2N=CHC6H2-3,5-(tBu)2-2-O)2}(NO3)]2(μ-OH)2 (4) as key intermediates during the catalytic cycle. Complex 2 was synthesized by reduction of 1 with 2,5-dimethyl-1,4-bis(trimethylsilyl)-1,4-diazacyclohexadiene. Bubbling O2 into a solution of 2 resulted in formation of the peroxo complex 3. This provides the first direct evidence for cerium-catalyzed oxidation of alcohols under an O2 atmosphere.

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Citations

Jul 4, 2017·Inorganic Chemistry·Jochen FriedrichReiner Anwander
Oct 30, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Ka-Chun Au-YeungWa-Hung Leung
Dec 21, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Polly L ArnoldAlexandra M Z Slawin
Dec 11, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Padmini Sahoo, Moumita Majumdar

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