Abstract
The mechanisms of double synchronous proton transfer in associates of formic acid with solvent molecules of the HC(O)OH⋯X (X = CH4, NH3, H2O, or HF) and HC(O)OH⋯FH⋯Y (Y = CH3F, NH2F, HOF, F2, or HF) types have been studied by anab initio (SCF/3G) method. The calculated activation barriers of the reactions are 78.52, 17.72, 9.91, and 7.06 kcal mol−1 in the former case and 120.1, 259.4, 228.7, 182.8, and 0.35 kcal mol−1 in the latter case. In the latter case, simultaneously with the double transfer of protons, migration of two fluorine atoms along the chain of the associate occurs.
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Dedicated to Academician of the RAS N. S. Zefirov (on his 60th birthday).
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1690–1700, September, 1995.
The present work was carried out with financial support from the Russian Foundation for Basic Research (Project Nos. 93-03-4972 and 93-03-18692) and the International Science Foundation (Grant ISF RNJ 000).
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Minyaev, R.M., Minkin, V.I. Double proton shifts in associates of formic acid with CH4, NH3, H2O, CH3F, NH2F, HOF, and HF molecules. Russ Chem Bull 44, 1622–1632 (1995). https://doi.org/10.1007/BF01151280
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DOI: https://doi.org/10.1007/BF01151280