An o-Phenylene Bridged Noninnocent Bis-Azopyridyl Ligand and Its Copper Complexes: Synthesis, Characterization of Electron Transfer Events, and Use of the Cu Complexes for Oxidation of Alcohols

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 14, 2025

In this report, an o-phenylene-bridged tetradented redox-noninnocent bis-azopyridyl ligand [L] and its copper complexes [1] [2] were synthesized characterized. The electron transfer events of [L], as well [2], characterized by single-crystal X-ray structure determination, various spectroscopic studies, DFT calculations. While [[L]Cu(II)Cl2] has unreduced [[L]•-Cu(I)Cl] contains a one-electron-reduced [L]•- , which is antiferromagnetically coupled with the unpaired spin on Cu(II). Reduction one generated complex [2]•-, remained in electronically bistable situation form valence tautomers: [2A]•-, [[L]•-Cu(I)Cl]•- [2B]•-, [[L]2-Cu(II)Cl]•-. Further one-electron reduction [2]•- mixture Cu complexes: [2A]-, [[L]2-Cu(I)]- [2B]-, [[L]3•-Cu(II)]-. Complexes examined for catalytic oxidation alcohols. was more efficient than [1]. protocol highly versatile both primary secondary aromatic aliphatic Mechanistic investigations showed that [[L]•-Cu(I)OCH2Ph]•- (A) active catalyst, subsequently, through ligand-based redox events, acted catalyst over course reaction.

Language: Английский

Redox Noninnocent Copper(I) Complex Where Metal Is a Spectator and Ligand Is an Actor in the Glaser Coupling Reaction of Alkynes

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 28, 2024

An extended trisazo dipyridyl ligand,