A new organometallic rhodium(I) complex with dpp-bian ligand: Synthesis, structure and redox behaviour. (15th November 2019)

• Record Type: Journal Article
• Authors: Romashev, Nikolai F.; Gushchin, Artem L.; Fomenko, Iakov S.; Abramov, Pavel A.; Mirzaeva, Irina V.; Kompan'kov, Nikolay B.; Kal'nyi, Danila B.; Sokolov, Maxim N.
• Is Part Of: Polyhedron. Volume 173(2019)
• Publication Date: 2019-11-15
• Subjects: Rhodium -- Acenaphthene-1, 2-diimines -- Synthesis -- Cyclic voltammetry -- DFT calculations; Chemistry, Inorganic -- Periodicals; Chimie inorganique -- Périodiques; Organometaalverbindingen; Anorganische chemie; 546.05
• DOI: 10.1016/j.poly.2019.114110
• Languages: English
• ISSNs: 0277-5387

Abstract

Graphical abstract: A new organometallic square-pyramidal Rh(I) complex with redox active bis(imino)acenaphthene ligand has been synthesized and fully characterized. Abstract: 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 ·0.25H2 O 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, 1 H NMR, CV and DFT calculations. Cyclic voltammetry of 1 in acetonitrile (CH3 CN) showed two reversible one-electron redox waves at E 1/2 = −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 .