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

Ilya K. Mikhailov; Zufar N. Gafurov; Alexey A. Kagilev; Vladimir I. Morozov; Artyom O. Kantyukov; Ekaterina 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

doi:10.20944/preprints202307.2130.v1

A peer-reviewed article of this Preprint also exists.

Mikhailov, I.K.; Gafurov, Z.N.; Kagilev, A.A.; Morozov, V.I.; Kantyukov, A.O.; Zueva, E.M.; Ganeev, G.R.; Sakhapov, I.F.; Toropchina, A.V.; Litvinov, I.A.; Gurina, G.A.; Trifonov, A.A.; Sinyashin, O.G.; Yakhvarov, D.G. Redox Chemistry of Pt(II) Complex with Non-Innocent NHC Bis(Phenolate) Pincer Ligand: Electrochemical, Spectroscopic, and Computational Aspects. Catalysts 2023, 13, 1291. Mikhailov, I.K.; Gafurov, Z.N.; Kagilev, A.A.; Morozov, V.I.; Kantyukov, A.O.; Zueva, E.M.; Ganeev, G.R.; Sakhapov, I.F.; Toropchina, A.V.; Litvinov, I.A.; Gurina, G.A.; Trifonov, A.A.; Sinyashin, O.G.; Yakhvarov, D.G. Redox Chemistry of Pt(II) Complex with Non-Innocent NHC Bis(Phenolate) Pincer Ligand: Electrochemical, Spectroscopic, and Computational Aspects. Catalysts 2023, 13, 1291.

Abstract

A Pt(II) complex featuring chelating tridentate bis-aryloxide tetrahydropyrimidinium based N-heterocyclic carbene (NHC) was synthesized and characterized by using different techniques. The electrochemical properties of the complex were investigated by cyclic voltammetry as well as differential pulse voltammetry, which revealed 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 AgBF4. The combined UV-Vis/NIR- and EPR-spectroscopy studies supported by density functional theory (DFT) calculations suggest the formation of 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).

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

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