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. |
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| 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] |
| Copyright of Journal of the American Society for Mass Spectrometry is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.) | |
| Database: | Engineering Source |
| FullText | Text: Availability: 0 |
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| Header | DbId: egs DbLabel: Engineering Source An: 98882578 AccessLevel: 6 PubType: Academic Journal PubTypeId: academicJournal PreciseRelevancyScore: 0 |
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| Items | – Name: Title Label: Title Group: Ti Data: Gas-Phase Lithium Cation Basicity: Revisiting the High Basicity Range by Experiment and Theory. – Name: Author Label: Authors Group: Au Data: <searchLink fieldCode="AR" term="%22Mayeux%2C+Charly%22">Mayeux, Charly</searchLink><relatesTo>1</relatesTo><i> mayeux@ut.ee</i><br /><searchLink fieldCode="AR" term="%22Burk%2C+Peeter%22">Burk, Peeter</searchLink><relatesTo>1</relatesTo><i> peeter.burk@ut.ee</i><br /><searchLink fieldCode="AR" term="%22Gal%2C+Jean-Francois%22">Gal, Jean-Francois</searchLink><relatesTo>2</relatesTo><br /><searchLink fieldCode="AR" term="%22Kaljurand%2C+Ivari%22">Kaljurand, Ivari</searchLink><relatesTo>1</relatesTo><i> ivari.kaljurand@ut.ee</i><br /><searchLink fieldCode="AR" term="%22Koppel%2C+Ilmar%22">Koppel, Ilmar</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Leito%2C+Ivo%22">Leito, Ivo</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Sikk%2C+Lauri%22">Sikk, Lauri</searchLink><relatesTo>1</relatesTo> – Name: TitleSource Label: Source Group: Src Data: <searchLink fieldCode="JN" term="%22Journal+of+the+American+Society+for+Mass+Spectrometry%22">Journal of the American Society for Mass Spectrometry</searchLink>. Nov2014, Vol. 25 Issue 11, p1962-1973. 12p. – Name: Subject Label: Subjects Group: Su Data: <searchLink fieldCode="DE" term="%22Gas+phase+reactions%22">Gas phase reactions</searchLink><br /><searchLink fieldCode="DE" term="%22Lithium+ions%22">Lithium ions</searchLink><br /><searchLink fieldCode="DE" term="%22Proton+transfer+reactions%22">Proton transfer reactions</searchLink><br /><searchLink fieldCode="DE" term="%22Ligands+%28Chemistry%29%22">Ligands (Chemistry)</searchLink><br /><searchLink fieldCode="DE" term="%22Tetrahydrofuran%22">Tetrahydrofuran</searchLink><br /><searchLink fieldCode="DE" term="%22Pyridine%22">Pyridine</searchLink> – Name: Abstract Label: Abstract Group: Ab Data: 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] – Name: AbstractSuppliedCopyright Label: Group: Ab Data: <i>Copyright of Journal of the American Society for Mass Spectrometry is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.) |
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| RecordInfo | BibRecord: BibEntity: Identifiers: – Type: doi Value: 10.1007/s13361-014-0970-4 Languages: – Code: eng Text: English PhysicalDescription: Pagination: PageCount: 12 StartPage: 1962 Subjects: – SubjectFull: Gas phase reactions Type: general – SubjectFull: Lithium ions Type: general – SubjectFull: Proton transfer reactions Type: general – SubjectFull: Ligands (Chemistry) Type: general – SubjectFull: Tetrahydrofuran Type: general – SubjectFull: Pyridine Type: general Titles: – TitleFull: Gas-Phase Lithium Cation Basicity: Revisiting the High Basicity Range by Experiment and Theory. Type: main BibRelationships: HasContributorRelationships: – PersonEntity: Name: NameFull: Mayeux, Charly – PersonEntity: Name: NameFull: Burk, Peeter – PersonEntity: Name: NameFull: Gal, Jean-Francois – PersonEntity: Name: NameFull: Kaljurand, Ivari – PersonEntity: Name: NameFull: Koppel, Ilmar – PersonEntity: Name: NameFull: Leito, Ivo – PersonEntity: Name: NameFull: Sikk, Lauri IsPartOfRelationships: – BibEntity: Dates: – D: 01 M: 11 Text: Nov2014 Type: published Y: 2014 Identifiers: – Type: issn-print Value: 10440305 Numbering: – Type: volume Value: 25 – Type: issue Value: 11 Titles: – TitleFull: Journal of the American Society for Mass Spectrometry Type: main |
| ResultId | 1 |
