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Rhodium(III) Complexes Featuring Coordinated CF3 Appendages.

Jack Emerson-King1, Ivan Prokes1, Adrian B Chaplin1

  • 1Department of Chemistry, University of Warwick, Gibbet Hill Road, Coventry, CV4 7AL, UK.

Chemistry (Weinheim an Der Bergstrasse, Germany)
|March 16, 2019
PubMed
Summary

Researchers synthesized rhodium 2,2'-biphenyl complexes with unique intramolecular dative bonding. This interaction involves the trifluoromethyl group, confirmed by X-ray diffraction and NMR spectroscopy, revealing novel rhodium-fluorine contacts.

Keywords:
coordination chemistryfluorinated ligandslow-coordinate complexesphosphane ligandsrhodium

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Area of Science:

  • Organometallic Chemistry
  • Coordination Chemistry
  • Fluorine Chemistry

Background:

  • Rhodium complexes are crucial in catalysis and materials science.
  • Trifluoromethyl groups are typically considered inert and weakly coordinating.
  • Intramolecular interactions can significantly alter complex properties.

Purpose of the Study:

  • To synthesize and characterize a series of rhodium 2,2iphenyl complexes.
  • To investigate intramolecular dative bonding involving the trifluoromethyl group.
  • To provide evidence for these interactions in both solid and solution states.

Main Methods:

  • Synthesis of homologous rhodium 2,2iphenyl complexes.
  • Solid-state characterization using X-ray diffraction.
  • Solution-state analysis using Nuclear Magnetic Resonance (NMR) spectroscopy.

Main Results:

  • Successful synthesis of rhodium complexes featuring intramolecular Rh-F dative bonds.
  • X-ray diffraction confirmed Rh-F contacts (2.36-2.45 Å) in the solid state.
  • NMR spectroscopy revealed hindered C-CF3 bond rotation and characteristic couplings (¹JRhF, ²JPF) in solution.

Conclusions:

  • The trifluoromethyl group can participate in intramolecular dative bonding with rhodium.
  • These interactions are stable and detectable in both crystalline and solution phases.
  • This work expands the understanding of trifluoromethyl group reactivity in organometallic complexes.