Origin of Compressed Jahn−Teller Octahedra in Sterically Strained Manganese(III) Complexes

A method is presented that enables the bond length changes resulting from the Jahn−Teller interaction to be predicted from a knowledge of the angular geometry of the complex and the identity of the ligators. The calculation of the energy minimum within the subspace of the Jahn−Teller active e skelet...

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Bibliographic Details
Published in:Inorganic chemistry 2008-01, Vol.47 (2), p.448-453
Main Author: Tregenna-Piggott, Philip L. W
Format: Article
Language:English
Subjects:
Bonding
Compressed
Distortion
Ligands
Manganese - chemistry
Mathematical models
Models, Molecular
Molecular Conformation
Molecular structure
Origins
Potential energy
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Summary:A method is presented that enables the bond length changes resulting from the Jahn−Teller interaction to be predicted from a knowledge of the angular geometry of the complex and the identity of the ligators. The calculation of the energy minimum within the subspace of the Jahn−Teller active e skeletal mode proceeds by diagonalization of the potential energy component of the cubic E⊗e Jahn−Teller problem, incorporating low-symmetry distortions by way of angular overlap model calculations. The theory is applied to a series of manganese(III) complexes formed with tetradentate tripodal ligands that largely dictate the angular coordinates. A good account of the contrasting molecular structures is obtained by allowing the σ-bonding strength to vary according to expectations based upon the spectrochemical series.
ISSN:0020-1669
1520-510X
DOI:10.1021/ic700968q