Failure of ESI Spectra to Represent Metal-Complex Solution Composition: A Study of Lanthanide–Carboxylate Complexes
2014
McDonald, Luther W. | Campbell, James A. | Clark, Sue B.
Electrospray ionization-mass spectrometry (ESI-MS) shows great promise as a rapid method to identify metal–ligand complexes in solution. However, its application for quantitative determination of the distribution of species present in complicated equilibria is still in its infancy, and a direct correlation between ions observed in the gas phase and species expected in solution must be made with caution. The present work focuses on a seemingly simple system; the complexation of lanthanide cations with the acetate ligand. Using a high resolution quadrupole time-of-flight mass spectrometer, ions created by electrospray of solutions containing trivalent neodymium and acetate were identified. The gas phase distribution of species was compared to the solution phase speciation predicted using thermodynamic complexation constants. Apparent gas phase speciation diagrams were constructed as a function of solution conditions and fragmentation potential. Despite the expected variability of metal–ligand complexes as solution conditions change, the observed gas phase speciation was independent of the metal to ligand ratio but dependent on the operating conditions of the ESI-MS.
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