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Uranyl complexation by monodentate nitrogen donor ligands. A relativistic density functional study
Author(s) -
Zakharieva Olga,
Kremleva Alena,
Krüger Sven,
Rösch Notker
Publication year - 2011
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.22483
Subject(s) - uranyl , chemistry , denticity , pyridine , density functional theory , methylamine , ligand (biochemistry) , aqueous solution , nitrogen , trans effect , medicinal chemistry , inorganic chemistry , crystallography , computational chemistry , ion , organic chemistry , crystal structure , biochemistry , receptor
To examine the interaction of uranyl with nitrogen containing groups of humic substances, the model complexes [UO 2 (H 2 O) 4 L N ] 2+ , L N = NH 2 CH 3 , N(CH 3 ) 3 , and NC 5 H 5 in aqueous solution were studied computationally with an all‐electron relativistic density functional method. Results are compared with the corresponding penta‐aqua complex of uranyl. Although pyridine coordinates with about the same strength as L = H 2 O, methylamine binds ∼10 kJ mol −1 stronger and trimethylamine ∼40 kJ mol −1 weaker than a fifth aqua ligand. Yet, each of these ligands L N donates about the same amount of charge to uranyl as L = H 2 O. UN bonds are ∼10 pm longer than the UO bonds of the aqua ligands. From the present model results, one does not expect that, when compared with carboxyl groups, monodentate N‐containing functional groups contribute significantly to uranyl complexation by humic substances. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011