Modeling of the various minima on the potential energy surface of bispidine copper(II) complexes : a further test for ligand field molecular mechanics
Bentz, Alexander, Comba, Peter, Deeth, Robert J., Kerscher, Marion, Seibold, Bjoern and Wadepohl, Hubert. (2008) Modeling of the various minima on the potential energy surface of bispidine copper(II) complexes : a further test for ligand field molecular mechanics. Inorganic Chemistry, Vol.47 (No.20). pp. 9518-9527. ISSN 0020-1669Full text not available from this repository.
Official URL: http://dx.doi.org/10.1021/ic8011052
Copper(II) complexes of bispidines (bispidine = tetra-, penta-, or hexadentate ligand, based on the 3,7-diazabicyclo[3.3.1]nonane backbone) display several isomeric forms. Depending on the substitution pattern of the bispidine and the type of coligands used, the structure elongates along one of the three potential Jahn-Teller axes. In an effort to develop a computational tool which can predict which isomer is observed, 23 bispidine-copper(II) complexes with 19 different ligands are analyzed theoretically by ligand field molecular mechanics (LFMM). With two exceptions, the lowest-energy LFMM structure and the experimental solid-state structure agree concerning the Jahn-Teller axis. However, in most cases and especially for six-coordinate complexes, LFMM predicts a second local minimum within a few kilojoules per mole. Although detailed analysis reveals that the current force field is too "stiff", reasonable quantitative reproduction of the structural data is achieved with Cu-L bond length root mean square (rms) deviations for nine complexes of 0.05 angstrom or less and with 20 reproduced to a rms deviation of 0.1 angstrom or less. Across all of the complexes, the Cu-amine and Cu-pyridyl bond length rms deviations are 0.07 and 0.12 angstrom, respectively.
|Item Type:||Journal Article|
|Subjects:||Q Science > QD Chemistry|
|Divisions:||Faculty of Science > Chemistry|
|Library of Congress Subject Headings (LCSH):||Ligand field theory, Molecular structure, Jahn-Teller effect, Molecules -- Models, Copper, Potential energy surfaces, Transition metal complexes|
|Journal or Publication Title:||Inorganic Chemistry|
|Publisher:||American Chemical Society|
|Official Date:||20 October 2008|
|Number of Pages:||10|
|Page Range:||pp. 9518-9527|
|Funder:||Deutsche Forschungsgemeinschaft (DFG), Chemical Computing Group, Engineering and Physical Sciences Research Council (EPSRC)|
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