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Related Experiment Videos

Terminally coordinated AsS and PS ligands.

Gábor Balázs1, Jennifer C Green, Manfred Scheer

  • 1Institut für Anorganische Chemie der Universität Regensburg, 93040 Regensburg, Germany. gabor.balazs@chemie.uni-regensburg.de

Chemistry (Weinheim an Der Bergstrasse, Germany)
|September 6, 2006
PubMed
Summary

New tungsten complexes featuring arsenic-sulfur and phosphorus-sulfur bonds were synthesized. Density functional theory calculations reveal double bond character for W-E and E-S bonds, suggesting unique electronic structures.

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Area of Science:

  • Organometallic Chemistry
  • Inorganic Chemistry
  • Computational Chemistry

Background:

  • Tungsten complexes with group 15 elements (E=P, As, Sb) and chalcogens (S) are of interest for their unique bonding.
  • Understanding the electronic structure and bonding in these complexes is crucial for predicting their reactivity and properties.

Purpose of the Study:

  • To synthesize and characterize novel terminal arsenic-sulfur (AsS) and phosphorus-sulfur (PS) tungsten complexes.
  • To investigate the nature of the W-E and E-S bonds using advanced computational methods.
  • To analyze the electronic structure and polarity of the synthesized complexes.

Main Methods:

  • Synthesis of tungsten-chalcogenide complexes via reaction with cyclohexene sulfide.
  • Characterization using density functional theory (DFT) calculations.

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  • Analysis of bonding through fragment calculations and Natural Bond Orbital (NBO) analysis.
  • Investigation of complex polarity using Hirshfeld charge analysis.

    • Main Results:

    • Successful synthesis of terminal AsS and PS tungsten complexes, [(N(3)N)W(ES)].
    • DFT and NBO analyses indicate significant double bond character (bond order ~2) for both W-E and E-S bonds.
    • The pi system is best described by two three-center, four-electron bonds.
    • Polarity studies show slight polarization in AsS and PS complexes, and moderate polarization towards sulfur in the SbS analogue.

    Conclusions:

    • The synthesized tungsten complexes exhibit strong W-E and E-S bonding, best described as having double bond character.
    • Computational analyses provide detailed insights into the electronic structure and bonding modes within these unique organometallic compounds.
    • The findings contribute to the understanding of bonding in low-coordinate main group element complexes with transition metals.