Pathways of the reactions of nucleophilic addition of H2O and HF molecules to formaldehyde in the gas phase and in the complex with formic acid:ab initio calculations |
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Authors: | R M Minyaev A G Starikov E A Lepin |
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Institution: | (1) Institute of Physical and Organic Chemistry, Rostov State University, 194/2 prosp. Stachki, 344090 Rostov-on-Don, Russian Federation |
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Abstract: | The gradient pathways of the reactions of nucleophilic addition of H2O and HF molecules to formaldehyde in the gas phase and in the XH…H2CO…HC(O)OH complex (X=OH, F) were calculated by theab initio RHF/6-31G**, MP2(fc)/6-31G**, and MP2(full)/6-311++G** methods. Both reactions proceed concertedly. The formation of H-bonded bimolecular pre-reaction complexes is the initial
stage of the gas-phase reactions; at the same time, no indications of the formation of stable π-complexes were found on the
potential energy surfaces of systems under study. The calculated energy barriers to the gasphase reactions exceed 40 kcal
mol−1, while those to reactions in the complex XH…H2CO…HC(O)OH (X=OH, F) become more than halved.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2146–2154, November, 1998. |
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Keywords: | ab initio calculations nucleophilic addition reaction pathway water hydrogen fluoride formaldehyde formic acid catalytic power |
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