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Electronic Structure of Organometallic Compounds

  1. Thomas A. Albright

Published Online: 15 MAR 2006

DOI: 10.1002/0470862106.ia073

Encyclopedia of Inorganic Chemistry

Encyclopedia of Inorganic Chemistry

How to Cite

Albright, T. A. 2006. Electronic Structure of Organometallic Compounds. Encyclopedia of Inorganic Chemistry. .

Author Information

  1. University of Houston, Houston, TX, USA

Publication History

  1. Published Online: 15 MAR 2006


A brief treatment of the concept of orbital interaction is given, particularly in reference to the transition metal-ligand bond. This is then applied to the σ splitting pattern for the MLn series where n = 6, 5, 4 (square planar and tetrahedral), 3, and 2 cases. Here M is a transition metal and L is a generic ligand with a σ donor function. A description is given for how the splitting pattern is modified when one or more of the ligands have π acceptor or donor functions. Several examples illustrate how symmetry can sometimes create modification to the normal electron counting rules. A detailed discussion is given of how to create the important valence orbitals of an MLn fragment and several examples are given of their use to build up the orbitals of large organometallic molecules. Finally, a detailed discussion is given of the construction and use of the isolobal analogy.


  • perturbation theory;
  • fragment orbitals;
  • isolobal analogy;
  • SALC;
  • polyene-MLn complexes;
  • MO theory;
  • electron counting;
  • M[BOND]L bonding