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Group 9 Chalcogenometalates.

Thomas E. Albrecht-Schmitt1, James A. Ibers

  • 1Department of Chemistry, Northwestern University, Evanston, Illinois 60208-3113.

Inorganic Chemistry
|December 4, 1996
PubMed
Summary
This summary is machine-generated.

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New iridium and rhodium complexes with polyselenide ligands were synthesized and characterized. These complexes exhibit temperature-dependent conformational changes, providing insights into their dynamic behavior and thermodynamic properties.

Area of Science:

  • Coordination Chemistry
  • Organometallic Chemistry
  • Materials Science

Background:

  • Polyselenide ligands offer unique coordination modes and electronic properties.
  • Iridium and rhodium complexes are valuable in catalysis and materials science.
  • Understanding the structural and dynamic behavior of these complexes is crucial.

Purpose of the Study:

  • To synthesize and characterize novel iridium and rhodium complexes featuring polyselenide ligands.
  • To investigate the structural features and conformational dynamics of these new compounds.
  • To determine the thermodynamic parameters governing temperature-dependent transformations.

Main Methods:

  • Synthesis of iridium and rhodium complexes via reactions with polyselenide anions.

Related Experiment Videos

  • Structural characterization using X-ray crystallography.
  • Spectroscopic analysis, including 77Se NMR spectroscopy for dynamic studies.

    • Main Results:

    • Three new iridium complexes, [K(18-crown-6)](3)[Ir(Se4)(3)] (1), [K(2.2.2-cryptand)](3)[Ir(Se4)(3)].C6H5CH3 (2), and [K(18-crown-6)(DMF)(2)][Ir(NCCH3)(2)(Se4)(2)] (3), were successfully prepared and structurally elucidated.
    • Complexes 1 and 2 feature distorted octahedral Ir(III) centers chelated by three Se4(2-) ligands, existing as racemates.
    • Temperature-dependent 77Se NMR studies revealed conformational transformations in [Ir(Se4)(3)](3)(-) and [Rh(Se4)(3)](3)(-) anions, with determined thermodynamic parameters (ΔH and ΔS).

    Conclusions:

    • Novel coordination compounds incorporating polyselenide ligands with iridium and rhodium have been synthesized.
    • The structural diversity and conformational flexibility of these complexes were demonstrated.
    • The study provides valuable thermodynamic data on the dynamic behavior of these unique inorganic complexes.