A new organometallic rhodium(I) complex with dpp-bian ligand: Synthesis, structure and redox behaviour
2019; Elsevier BV; Volume: 173; Linguagem: Inglês
10.1016/j.poly.2019.114110
ISSN1873-3719
AutoresN. F. Romashev, Artem L. Gushchin, Iakov S. Fomenko⧫, Pavel A. Abramov⧫, И.В. Мирзаева, Nikolay B. Kompankov, Danila B. Kal’nyi, Maxim N. Sokolov⧫,
Tópico(s)Metal complexes synthesis and properties
ResumoReaction 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 RhCl 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 RhCl distance and interpret the reduction sequence of 1.
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