Redox Chemistry of Pt(II) Complex with Non-Innocent NHC Bis(Phenolate) Pincer Ligand: Electrochemical, Spectroscopic, and Computational Aspects

A Pt(II) complex bearing chelating tridentate bis-aryloxide tetrahydropyrimidinium-based N-heterocyclic carbene (NHC) was synthesized and characterized by using different techniques. Both cyclic voltammetry and differential pulse voltammetry were used to study the electrochemical properties of the c...

Full description

Bibliographic Details
Main Authors: Ilya K. Mikhailov, Zufar N. Gafurov, Alexey A. Kagilev, Vladimir I. Morozov, Artyom O. Kantyukov, Ekaterina M. Zueva, Gumar R. Ganeev, Ilyas F. Sakhapov, Asiya V. Toropchina, Igor A. Litvinov, Galina A. Gurina, Alexander A. Trifonov, Oleg G. Sinyashin, Dmitry G. Yakhvarov
Format: Article
Language:English
Published: MDPI AG 2023-09-01
Series:Catalysts
Subjects:
Online Access:https://www.mdpi.com/2073-4344/13/9/1291
Description
Summary:A Pt(II) complex bearing chelating tridentate bis-aryloxide tetrahydropyrimidinium-based N-heterocyclic carbene (NHC) was synthesized and characterized by using different techniques. Both cyclic voltammetry and differential pulse voltammetry were used to study the electrochemical properties of the complex, revealing two reversible one-electron oxidation processes. The chemical generation and isolation of one-electron-oxidized species were performed oxidizing the initial complex by means of AgBF<sub>4</sub>. A combination of spectroscopic (UV-Vis/NIR- and EPR-) and theoretical (density functional theory (DFT)) studies suggests the formation of a Pt(II)-phenoxyl radical complex. The latter open-shell derivative was structurally characterized by means of X-ray diffraction analysis. Finally, the neutral platinum complex was tested as a mediator in the process of electrocatalytic oxidation of 2-(methylamino)ethanol (MEA).
ISSN:2073-4344