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Nonoctahedral structures.

Konrad Seppelt1

  • 1Institut für Anorganische und Analytische Chemie, Freie Universität Berlin, D-14195 Berlin, Germany.

Accounts of Chemical Research
|February 19, 2003
PubMed
Summary
This summary is machine-generated.

Six-coordinate molecules deviate from octahedral geometry due to Jahn-Teller distortion or electron pair effects. Recent studies show d(0) and d(1) complexes with sigma ligands adopt trigonal prismatic structures.

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Area of Science:

  • Inorganic Chemistry
  • Computational Chemistry

Background:

  • Six-coordinate molecules typically exhibit octahedral geometry.
  • Deviations from octahedral geometry are known, including Jahn-Teller distortions and steric effects of nonbonding electron pairs (e.g., XeF(6)).

Purpose of the Study:

  • To investigate the non-octahedral geometries observed in six-coordinate d(0) and d(1) complexes with sigma-only ligands.
  • To explain the structural preferences using theoretical models.

Main Methods:

  • Analysis of six-coordinate d(0) and d(1) complexes with sigma-only ligands.
  • Application of simple molecular orbital (MO) and valence bond (VB) models.

Main Results:

  • Six-coordinate d(0) and d(1) complexes with sigma-only ligands, such as Mo(CH3)(6), are not octahedral.

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  • These complexes adopt trigonal prismatic or C(3v) distorted trigonal prismatic geometries.
  • The observed geometries can be rationalized using MO and VB theories.

    • Conclusions:

    • The deviation from octahedral geometry in these specific complexes is a predictable outcome of their electronic configuration and ligand type.
    • Simple theoretical models are sufficient to explain the structural preferences, highlighting the importance of electronic factors in determining molecular geometry.