Issue 12, 2024

Amphoteric reactivity of a putative Cu(ii)-mCPBA intermediate

Abstract

In copper-based enzymes, Cu-hydroperoxo/alkylperoxo species are proposed as key intermediates for their biological activity. A vast amount of literature is available on the functional and structural mimics of enzymatic systems with heme and non-heme ligand frameworks to stabilize high valent metal intermediates, mostly at low temperatures. Herein, we report a reaction between [CuI(NCCH3)4]+ and meta-chloroperoxybenzoic acid (mCPBA) in CH3CN that produces a putative CuII(mCPBA) species (1). 1 was characterized by UV/Vis, resonance Raman, and EPR spectroscopies. 1 can catalyze both electrophilic and nucleophilic reactions, demonstrating its amphoteric behavior. Additionally, 1 can also conduct electron transfer reactions with a weak reducing agent such as diacetyl ferrocene, making it one of the reactive copper-based intermediates. One of the most important aspects of the current work is the easy synthesis of a CuII(mCPBA) adduct with no complicated ligands for stabilization. Over time, 1 decays to form a CuII paddle wheel complex (2) and is found to be unreactive towards substrate oxidation.

Graphical abstract: Amphoteric reactivity of a putative Cu(ii)-mCPBA intermediate

Supplementary files

Article information

Article type
Paper
Submitted
09 Nov 2023
Accepted
17 Feb 2024
First published
20 Feb 2024

Dalton Trans., 2024,53, 5401-5406

Amphoteric reactivity of a putative Cu(II)-mCPBA intermediate

R. Kumar, A. Maji, B. Biswas and A. Draksharapu, Dalton Trans., 2024, 53, 5401 DOI: 10.1039/D3DT03747A

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements