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Modeling of the Various Minima on the Potential Energy Surface of Bispidine Copper(II) Complexes: A Further Test for Ligand Field Molecular Mechanics.
- Source :
-
Inorganic Chemistry . 10/20/2008, Vol. 47 Issue 20, p9518-9527. 10p. 1 Diagram, 3 Charts, 1 Graph. - Publication Year :
- 2008
-
Abstract
- 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-TeIler 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 Å or less and with 20 reproduced to a rms deviation of 0.1 A or less. Across all of the complexes, the Cu-amine and Cu-pyridyl bond length rms deviations are 0.07 and 0.12 Å, respectively. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 00201669
- Volume :
- 47
- Issue :
- 20
- Database :
- Academic Search Index
- Journal :
- Inorganic Chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 34978219
- Full Text :
- https://doi.org/10.1021/ic8011052