Electrochemical generation and in situ EPR- and UV–vis- observation of aminyl-radical diarylamido/bis(phosphine) pincer complexes of Ni, Pd and Ptстатья
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Дата последнего поиска статьи во внешних источниках: 10 апреля 2024 г.
Аннотация:The electrochemical properties of bis[2-(di-i-propylphosphino)-4-methylphenyl]amido complexes [(PNP)MCl] of Ni, Pd and Pt have been investigated by experimental electrochemical methods involving cyclic voltammetry (CV), in situ UV–vis- and EPR-spectroelectrochemistry, and density functional theory (DFT) calculations. A combination of spectroscopic and theoretical techniques suggests the formation of aminyl-radical complexes as a result of the electrooxidation process. The photophysical behavior of the electrochemically generated species was studied by in situ EPR measurements with photoexcitation, which revealed the formation of free aminyl radical through the cleavage of the ligand–metal bonds. Finally, the electrochemical generation and spectroelectrochemical studies of the hydride derivative [(PNP)PdH] allow the determination of the aminyl-radical hydride complex [(PNP)PdH][BF4], which has been generated with 33 % yield.