Reactivity of Mononuclear Alkylperoxo Copper(II) Complex. O−O Bond Cleavage and C−H Bond Activation

Abstract

A detailed reactivity study has been carried out for the first time on a new mononuclear alkylperoxo copper(II) complex, which is generated by the reaction of copper(II) complex supported by the bis(pyridylmethyl)amine tridentate ligand containing a phenyl group at the 6-position of the pyridine donor groups and cumene hydroperoxide (CmOOH) in CH3CN. The cumylperoxo copper(II) complex thus obtained has been found to undergo homolytic cleavage of the O-O bond and induce C-H bond activation of exogenous substrates, providing important insights into the catalytic mechanism of copper monooxygenases.

Interaction of copper(II) with the non-steroidal anti-inflammatory drugs naproxen and diclofenac: Synthesis, structure, DNA- and albumin-binding

“…2(A). The EPR signals of powder samples of the complexes exhibit a main derivative at g ⊥ = 2.06 and a broad peak at g || = 2.25 close to the values expected for octahedral Cu(II) sites [75]. This was further verified from the solution studies where in the case of complex 1 it was possible to resolve the hyperfine pattern ( Fig.…”

Copper(I)‐Dioxygen Adducts and Copper Enzyme Mechanisms

“…[47] Using the radical trapping agent 5,5-dimethyl-1-pyrroline-N-oxide (DMPO), the putative copper(II) oxyl species formed could be trapped and characterized by ESI-MS and EPR spectroscopy. Without the radical trap, oxidation of N -methyl-9,10-dihydroacridine (AcrH 2 ) and 1,4-cyclohexadiene to N -methylacridinium and benzene, respectively, occurred.…”

Elaboration of copper–oxygen mediated C–H activation chemistry in consideration of future fuel and feedstock generation

“…However, in one study, Itoh and co-workers [61] provided compelling evidence for the generation of Cp , produced from O-O homolysis of a Cu II -OOR complex, leading to a substrate C-H oxygenation. In a DFT computational study, Beckham and co-workers [62] suggest that net C–H hydroxylation in fungal LPMOs may occur by generation of Cp (of course starting from Cu I -O 2 chemistry).…”