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Gas-Phase Lithium Cation Basicity: Revisiting the High Basicity Range by Experiment and Theory.

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Title: Gas-Phase Lithium Cation Basicity: Revisiting the High Basicity Range by Experiment and Theory.
Authors: Mayeux, Charly1 mayeux@ut.ee, Burk, Peeter1 peeter.burk@ut.ee, Gal, Jean-Francois2, Kaljurand, Ivari1 ivari.kaljurand@ut.ee, Koppel, Ilmar1, Leito, Ivo1, Sikk, Lauri1
Source: Journal of the American Society for Mass Spectrometry. Nov2014, Vol. 25 Issue 11, p1962-1973. 12p.
Subjects: Gas phase reactions, Lithium ions, Proton transfer reactions, Ligands (Chemistry), Tetrahydrofuran, Pyridine
Abstract: According to high level calculations, the upper part of the previously published FT-ICR lithium cation basicity (LiCB at 373 K) scale appeared to be biased by a systematic downward shift. The purpose of this work was to determine the source of this systematic difference. New experimental LiCB values at 373 K have been measured for 31 ligands by proton-transfer equilibrium techniques, ranging from tetrahydrofuran (137.2 kJ mol) to 1,2-dimethoxyethane (202.7 kJ mol). The relative basicities (ΔLiCB) were included in a single self-consistent ladder anchored to the absolute LiCB value of pyridine (146.7 kJ mol). This new LiCB scale exhibits a good agreement with theoretical values obtained at G2(MP2) level. By means of kinetic modeling, it was also shown that equilibrium measurements can be performed in spite of the formation of Li bound dimers. The key feature for achieving accurate equilibrium measurements is the ion trapping time. The potential causes of discrepancies between the new data and previous experimental measurements were analyzed. It was concluded that the disagreement essentially finds its origin in the estimation of temperature and the calibration of Cook's kinetic method. [Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]
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Database: Engineering Source
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Abstract:According to high level calculations, the upper part of the previously published FT-ICR lithium cation basicity (LiCB at 373 K) scale appeared to be biased by a systematic downward shift. The purpose of this work was to determine the source of this systematic difference. New experimental LiCB values at 373 K have been measured for 31 ligands by proton-transfer equilibrium techniques, ranging from tetrahydrofuran (137.2 kJ mol) to 1,2-dimethoxyethane (202.7 kJ mol). The relative basicities (ΔLiCB) were included in a single self-consistent ladder anchored to the absolute LiCB value of pyridine (146.7 kJ mol). This new LiCB scale exhibits a good agreement with theoretical values obtained at G2(MP2) level. By means of kinetic modeling, it was also shown that equilibrium measurements can be performed in spite of the formation of Li bound dimers. The key feature for achieving accurate equilibrium measurements is the ion trapping time. The potential causes of discrepancies between the new data and previous experimental measurements were analyzed. It was concluded that the disagreement essentially finds its origin in the estimation of temperature and the calibration of Cook's kinetic method. [Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]
ISSN:10440305
DOI:10.1007/s13361-014-0970-4