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Pd(0) and Pt(0) metallocryptands encapsulating a spinning mercurous dimer.

Vincent J Catalano1, Mark A Malwitz, Bruce C Noll

  • 1Department of Chemistry, University of Nevada, Reno 89557, USA. vjc@unr.edu

Inorganic Chemistry
|December 10, 2002
PubMed
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New platinum and palladium complexes featuring a mercury dimer core were synthesized. These air-stable metallocryptands exhibit unique structural and photophysical properties, paving the way for novel materials.

Area of Science:

  • Coordination Chemistry
  • Organometallic Chemistry
  • Materials Science

Background:

  • Development of novel metal complexes with unique structural motifs.
  • Exploration of complexes containing mercury-metal bonds for advanced applications.

Purpose of the Study:

  • To synthesize and characterize novel platinum and palladium complexes incorporating a mercury dimer.
  • To investigate the structural, spectroscopic, and photophysical properties of these new compounds.

Main Methods:

  • Stoichiometric reaction of platinum or palladium precursors with 2,9-bis(diphenylphosphino)-1,10-phenanthroline and elemental mercury.
  • Characterization using multinuclear NMR spectroscopy ((31)P, (199)Hg, (195)Pt) and single-crystal X-ray diffraction.
  • Photophysical studies involving excitation and emission spectroscopy.

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Main Results:

  • Successful synthesis of air-stable, deep-red complexes [Pt(2)Hg(2)(P(2)phen)(3)](PF(6))(2) and [Pd(2)Hg(2)(P(2)phen)(3)](PF(6))(2).
  • X-ray diffraction confirmed a metallocryptand structure with a central Hg(2)(2+) unit and a Hg-Hg bond.
  • NMR spectroscopy indicated dynamic behavior of the Hg(2)(2+) unit and provided evidence for Pt-Hg and Pd-Hg interactions.
  • Complexes exhibited luminescence upon excitation at low energy bands.

Conclusions:

  • The study presents a novel class of metallocryptand complexes featuring a dinuclear mercury core stabilized by platinum or palladium.
  • The unique D(3) symmetric cage structure and observed Hg-Hg bonding are significant structural findings.
  • The complexes demonstrate interesting photophysical properties, suggesting potential for applications in materials science.