Work

Rivalling Self‐Oxidation and Aldehyde Deformylation by a Dinuclear Copper(II)‐Superoxide Complex

Year: 2025

Type: article

Abstract: In this researchwe report the reactivity of dimeric Cu2L2 (HL = 2‐{[[di(2‐pyridyl)methyl](methyl)amino]‐methyl}phenol) with KO2 in acetonitrile at −40 °C alone and in combination with 2‐phenylpropionaldehyde (2‐PPA) or cyclohexanecarboxaldehyde (CCA). The putative Cu2‐superoxide intermediate undergoes self‐oxidation at the ligand‐sites in the absence of the aldehyde substrate. Instead, it acts as an efficient nucleophilic oxidative deformylation agent, via Baeyer–Villiger oxidation mechanism engaged by the aldehydes which behave as protective agents neutralizing parasitic ligand degradation by the superoxide. Electrospray ionization mass spectrometry analysis (ESI‐MS) after warming up the solution to room temperature, confirmed the formation of Cu2L2‐formate adducts along with acetophenone or cyclohexanone products. The cooperation between the two metal centres, one acting as binding site for the substrate and the other as active site for the superoxide activation was found to be fundamental for the aldehyde deformylation/oxidation mechanism and the overall complex stability.

Source: ChemCatChem

DOI: 10.1002/cctc.202500511

Authors: Andrea Squarcina, Marta Lovisari, Paolo Pirovano, Aidan R. McDonald, Marcella Bonchio

Institutions: University of Padua, Trinity College Dublin

Language: English

Topic: Metal-Catalyzed Oxygenation Mechanisms

Subfield: Inorganic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: hybrid

Estimated APC paid: $4,500

Funders: European Commission, NextGenerationEU