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Modeling the IR Spectra of Aqueous Metal Carboxylate Complexes: Correlation between Bonding Geometry and Stretching Mode Wavenumber Shifts
Author(s) -
Sutton Catherine C. R.,
da Silva Gabriel,
Franks George V.
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201406516
Subject(s) - carboxylate , denticity , wavenumber , aqueous solution , chemistry , metal , crystallography , infrared , computational chemistry , geometry , stereochemistry , organic chemistry , physics , optics , mathematics
A widely used principle is that shifts in the wavenumber of carboxylate stretching modes upon bonding with a metal center can be used to infer if the geometry of the bonding is monodentate or bidentate. We have tested this principle with ab initio modeling for aqueous metal carboxylate complexes and have shown that it does indeed hold. Modeling of the bonding of acetate and formate in aqueous solution to a range of cations was used to predict the infrared spectra of the metal‐carboxylate complexes, and the wavenumbers of the symmetric and antisymmetric vibrational modes are reported. Furthermore, we have shown that these shifts in wavenumber occur primarily due to how bonding with the metal changes the carboxylate CO bond lengths and O‐C‐O angle.