A. L. Gushchin, N. F. Romashev, A. A. Shmakova, P. A. Abramov, M. R. Ryzhikov, I. S. Fomenko, M. N. Sokolov, “Novel redox active rhodium(iii) complex with bis(arylimino)acenaphthene ligand: synthesis, structure and electrochemical studies”, Mendeleev Commun., 2020, Volume 30, Issue 1,Pages <nobr>81

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Communications

Novel redox active rhodium(iii) complex with bis(arylimino)acenaphthene ligand: synthesis, structure and electrochemical studies

A. L. Gushchin^ab, N. F. Romashev^ab, A. A. Shmakova^a, P. A. Abramov^abc, M. R. Ryzhikov^ab, I. S. Fomenko^a, M. N. Sokolov^ab

^a A.V. Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, Novosibirsk, Russian Federation
^b Novosibirsk State University, Novosibirsk, Russian Federation
^c South Ural State University (National Research University), Chelyabinsk, Russian Federation

Abstract: (Rhodium trichloride reacts with 1,2-bis[(2,6-diisopropylphenyl)imino] acenaphthene (dpp-bian) to afford new octahedral complex mer-[Rh(dpp-bian)(H₂O)Cl₃]·CH₂Cl₂. The CV of mer-[Rh(dpp-bian)(H₂O)Cl₃] in MeCN shows an irreversible reduction that corresponds to the Rh^III/Rh^I couple, followed by reversible or quasi-reversible cathodic waves assigned to reduction of the dpp-bian ligand. DFT calculations confirm the assignment of the redox processes and predict the elimination of two chloride ligands from axial positions upon two-electron reduction of mer-[Rh(dpp-bian)(H₂O)Cl₃] with the formation of a Rh^I square-planar complex [Rh^I(dpp-bian)(H₂O)Cl].

Keywords: rhodium, acenaphthene-1,2-diimines, crystal structure, cyclic voltammetry, DFT calculations, electrocatalyzed CO2 reduction.

Language: English

DOI: 10.1016/j.mencom.2020.01.027

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