Protic anions [H(B12X12)]- (X = F, Cl, Br, I) that act as Brønsted acids in the gas phase

Chemistry : a European Journal
Carsten JenneJonas Warneke

Abstract

The acidity of protic cations and neutral molecules has been studied extensively in the gas phase, and the gas-phase acidity has been established previously as a very useful measure of the intrinsic acidity of neutral and cationic compounds. However, no data for any anionic acids were available prior to this study. The protic anions [H(B12X12)](-) (X = F, Cl, Br, I) are expected to be the most acidic anions known to date. Therefore, they were investigated in this study with respect to their ability to protonate neutral molecules in the gas phase by using a combination of mass spectrometry and quantum-chemical calculations. For the first time it was shown that in the gas phase protic anions are also able to protonate neutral molecules and thus act as Brønsted acids. According to theoretical calculations, [H(B12I12)](-) is the most acidic gas-phase anion, whereas in actual protonation experiments [H(B12Cl12)](-) is the most potent gas-phase acidic anion for the protonation of neutral molecules. This discrepancy is explained by ion pairing and kinetic effects.

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Citations

Feb 28, 2017·Inorganic Chemistry·Philipp BertoccoChristoph Kirsch
May 31, 2017·Angewandte Chemie·Anja WiesnerSebastian Riedel
Apr 19, 2016·Chemical Communications : Chem Comm·Jonas WarnekeMarkus Plaumann
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Sep 4, 2020·Proceedings of the National Academy of Sciences of the United States of America·Jonas WarnekeJulia Laskin
Oct 6, 2020·Chemistry : a European Journal·Knut R AsmisQinqin Yuan
Aug 16, 2019·Journal of the American Society for Mass Spectrometry·Pei SuJulia Laskin
Jul 3, 2021·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Igor E GolubElena S Shubina
Feb 22, 2018·Inorganic Chemistry·Jonathan C AxtellAlexander M Spokoyny
Apr 20, 2019·Analytical Chemistry·Pei SuJulia Laskin
Sep 15, 2021·Journal of the American Chemical Society·Hendrik F T Klare, Martin Oestreich

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