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Infrared multiple‐photon dissociation spectroscopy of group II metal complexes with salicylate
Author(s) -
Dain Ryan P.,
Gresham Gary,
Groenewold Gary S.,
Steill Jeffrey D.,
Oomens Jos,
Stipdonk Michael J.
Publication year - 2011
Publication title -
rapid communications in mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.528
H-Index - 136
eISSN - 1097-0231
pISSN - 0951-4198
DOI - 10.1002/rcm.5053
Subject(s) - chemistry , infrared multiphoton dissociation , carboxylate , dissociation (chemistry) , density functional theory , metal , carboxylic acid , infrared spectroscopy , spectroscopy , tandem mass spectrometry , inorganic chemistry , photochemistry , mass spectrometry , crystallography , stereochemistry , computational chemistry , organic chemistry , physics , chromatography , quantum mechanics
Ion trap tandem mass spectrometry with collision‐induced dissociation, and the combination of infrared multiple‐photon dissociation (IRMPD) spectroscopy and density functional theory (DFT) calculations, were used to characterize singly charged, 1:1 complexes of Ca 2+ , Sr 2+ and Ba 2+ with salicylate. For each metal‐salicylate complex, the CID pathways are: (a) elimination of CO 2 and (b) formation of [MOH] + where M = Ca 2+ , Sr 2+ or Ba 2+ . DFT calculations predict three minima for the cation‐salicylate complexes which differ in the mode of metal binding. In the first, the metal ion is coordinated by O atoms of the (neutral) phenol and carboxylate groups of salicylate. In the second, the cation is coordinated by phenoxide and (neutral) carboxylic acid groups. The third mode involves coordination by the carboxylate group alone. The infrared spectrum for the metal‐salicylate complexes contains a number of absorptions between 1000 and 1650 cm –1 , and the best correlation between theoretical and experimental spectra is found for the structure that features coordination of the metal ion by phenoxide and the carbonyl O of the carboxylic acid group, consistent with the calculated energies for the respective species. Copyright © 2011 John Wiley & Sons, Ltd.