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Chelate effect: The importance of reorganization energy
Author(s) -
Davydova E. I.,
Sevastianova T. N.,
Timoshkin A. Y.,
Suvorov A. V.,
Frenking G.
Publication year - 2004
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.20094
Subject(s) - denticity , chemistry , chelation , halogen , density functional theory , ligand (biochemistry) , metal , computational chemistry , crystallography , stereochemistry , inorganic chemistry , organic chemistry , receptor , biochemistry , alkyl
Abstract The chelate effect has been theoretically studied at the Becke's three‐parameter exchange functional and the gradient‐corrected functional of Lee, Yang, and Paar/double‐ζ polarization level of theory. The influence of ligand, metal, and halogen nature on the chelate effect was analyzed for complexes of group 14 element tetrahalides with monodentate and bidentate nitrogen‐containing donors. It is shown that the large reorganization energy of the 2,2′‐bipyridine ligand (≈32 kJ mol ‐1 ) shadows the chelate effect. The same conclusion holds for other ligands, which undergo significant reorganization upon complex formation. 1,10‐Phenanthroline does not have such a large reorganization energy, and its complexes are therefore more stable in the gas phase than are complexes with bipyridine. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2004