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

Research output: Contribution to journalArticlepeer-review

3 Citations (Scopus)

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 1·0.25H2O 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.

Original languageEnglish
Article number114110
Number of pages9
JournalPolyhedron
Volume173
DOIs
Publication statusPublished - 15 Nov 2019

Keywords

  • Acenaphthene-1,2-diimines
  • Cyclic voltammetry
  • DFT calculations
  • Rhodium
  • Synthesis
  • Acenaphthene-1, 2-diimines
  • HYDROGENATION
  • DIIMINE NI(II) CATALYST
  • REACTIVITY
  • CRYSTAL-STRUCTURES
  • POLYMERIZATION
  • REDUCTION
  • SPECTROSCOPY
  • X-RAY
  • VALENCE TAUTOMERISM
  • METAL

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