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, 1954-. (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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