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PreprintCC BYChemRxiv

Anion effects on pKa values of organophosphonium salts in o-difluorobenzene and implications

  • Yunfei Liang1
  • Xiangmei Kong1
  • Zhenbo Guo1
  • Shanhui Zhu1
  • Jun Chen1
  • Tianfei Liu1,2
  • Jin-Pei Cheng3,4
4 affiliations
  1. 1State Key Laboratory of Elemento-organic Chemistry, Frontiers Science Center for New Organic Matter, College of Chemistry, Nankai University, Weijin Road No. 94, Tianjin, China, 300071
  2. 2Haihe Laboratory of Sustainable Chemical Transformations
  3. 3Department of Chemistry
  4. 4Tsinghua University
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Abstract

Herein, the anion effects on p K a values of organophosphonium salts in o -difluorobenzene are reported. Using the autoprotolysis constants of 2-(4-trifluoromethanesulfonato)phenylmalononitrile as an anchor, the p K a values of eight organophosphonium bistriflimides are experimentally determined in three polar fluorinated arenes via 31 P{ 1 H} NMR spectroscopic titration. Subsequently, the p K a values of eight corresponding organophosphonium tetrafluoroborates and eight corresponding organophosphonium tetraphenylborates soluble in o -difluorobenzene are further experimentally determined. These p K a values show significant differences due to different counter-anions. Further DFT calculations reveals that the anions BF 4 – and NTf 2 – in o-difluorobenzene form hydrogen-bonded contact ion pairs with organophosphonium cation, but BPh 4 – forms contact ion pairs via Coulombic interactions with it. In addition to providing important guidance for future improvement of DFT and AI for predicting p K a values and thermodynamic analyses in low dielectric constant solvents, this work also provides a more comprehensive understanding of anion effects in organic and inorganic X–H bond breaks and formations.

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Cite

BibTeXRIS
BibTeX
@misc{liang2026anion,
  title = {{Anion effects on pKa values of organophosphonium salts in o-difluorobenzene and implications}},
  author = {Yunfei Liang and Xiangmei Kong and Zhenbo Guo and Shanhui Zhu and Jun Chen and Tianfei Liu and Jin-Pei Cheng},
  howpublished = {ChemRxiv},
  year = {2026},
  month = sep,
  doi = {10.26434/chemrxiv.15008397/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008397/v1},
  note = {CC BY},
}
RIS
TY  - UNPB
TI  - Anion effects on pKa values of organophosphonium salts in o-difluorobenzene and implications
AU  - Yunfei Liang
AU  - Xiangmei Kong
AU  - Zhenbo Guo
AU  - Shanhui Zhu
AU  - Jun Chen
AU  - Tianfei Liu
AU  - Jin-Pei Cheng
PY  - 2026
DA  - 2026/09/07
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15008397/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008397/v1
AB  - Herein, the anion effects on p K a values of organophosphonium salts in o -difluorobenzene are reported. Using the autoprotolysis constants of 2-(4-trifluoromethanesulfonato)phenylmalononitrile as an anchor, the p K a values of eight organophosphonium bistriflimides are experimentally determined in three polar fluorinated arenes via 31 P{ 1 H} NMR spectroscopic titration. Subsequently, the p K a values of eight corresponding organophosphonium tetrafluoroborates and eight corresponding organophosphonium tetraphenylborates soluble in o -difluorobenzene are further experimentally determined. These p K a values show significant differences due to different counter-anions. Further DFT calculations reveals that the anions BF 4 – and NTf 2 – in o-difluorobenzene form hydrogen-bonded contact ion pairs with organophosphonium cation, but BPh 4 – forms contact ion pairs via Coulombic interactions with it. In addition to providing important guidance for future improvement of DFT and AI for predicting p K a values and thermodynamic analyses in low dielectric constant solvents, this work also provides a more comprehensive understanding of anion effects in organic and inorganic X–H bond breaks and formations.
ER  -