A new organometallic rhodium(I) complex with dpp-bian ligand: Synthesis, structure and redox behaviour

Nikolai F. Romashev, Artem L. Gushchin, Iakov S. Fomenko, Pavel A. Abramov, Irina V. Mirzaeva, Nikolay B. Kompan'kov, Danila B. Kal'nyi, Maxim N. Sokolov

Результат исследования: Научные публикации в периодических изданияхстатья

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Аннотация

Reaction of [{Rh(COD)}2(μ-Cl)2] with 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (dpp-bian) has afforded a new organometallic complex [Rh(COD)(dpp-bian)Cl] (1). The crystal structure of 1·0.25H2O was determined by X-ray single crystal analysis. The rhodium(I) ion has a distorted square-pyramidal coordination. The Rh[sbnd]Cl distance (2.5908 (12) Å) is rather long, indicating weak coordination of the chloride. Dissociation of chloride in solution to produce cationic [Rh(COD)(bian)]+ ([1-Cl]+) was confirmed by ESI-MS, 1H NMR, CV and DFT calculations. Cyclic voltammetry of 1 in acetonitrile (CH3CN) showed two reversible one-electron redox waves at E1/2 = −0.36 V and −1.18 V (versus Ag/AgCl) attributable to successive reduction of the dpp-bian ligand in [1-Cl]+. DFT calculations were performed to explain the anomalously long Rh[sbnd]Cl distance and interpret the reduction sequence of 1.

Язык оригиналаанглийский
Номер статьи114110
ЖурналPolyhedron
Том173
DOI
СостояниеОпубликовано - 15 ноя 2019

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