Infrared Multiple-Photon Dissociation spectroscopy of group II metal complexes with salicylate

Journal Article · Fri Jul 01 00:00:00 EDT 2011 · Rapid Communications in Mass Spectrometry

DOI:https://doi.org/10.1002/rcm.5053· OSTI ID:1021019

Dain, Ryan P; Gresham, Gary; Groenewold, Gary S; Steill, Jeffrey D; Oomens, Jos; van Stipdonk, Michael J

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 Ca2+, Sr2+ and Ba2+ with salicylate. For each metal-salicylate complex, the CID pathways are: (a) elimination of CO2 and (b) formation of [MOH]+ where M=Ca2+, Sr2+ or Ba2+. 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 – 1650 cm-1, and the best correlation between theoretical and experimental spectra for the structure that features coordination of the metal ion by phenoxide and the carbonyl group of the carboxylic acid group, consistent with calculated energies for the respective species.

• Research Organization: Idaho National Lab. (INL), Idaho Falls, ID (United States)
• Sponsoring Organization: USDOE
• DOE Contract Number: DE-AC07-05ID14517
• OSTI ID: 1021019
• Report Number(s): INL/JOU-11-21168; TRN: US201116%%667
• Journal Information: Rapid Communications in Mass Spectrometry, Vol. 25, Issue 13; ISSN 0951-4198
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ATOMS
CARBONYLS
CARBOXYLIC ACIDS
CATIONS
COMPLEXES
CORRELATIONS
DENSITY FUNCTIONAL METHOD
DISSOCIATION
IONS
MASS SPECTROSCOPY
METALS
PHENOL
SALICYLIC ACID
SPECTRA
SPECTROSCOPY
density functional theory
infrared spectroscopy
mass spectrometry
metal coordination complex
salicylate