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Issue 14, 1993
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Structure and acidity of carbamic acid, and its thio, dithio and sila dervatives

Abstract

An ab initio molecular orbital method (at the 6–31G** level of theory) has been used to study the molecular structure of carbamic acid, thiocarbamic O-acid, thiocarbamic S-acid, dithiocarbamic acid and silacarbamic acid, respectively. The total internal energy of the molecules investigated was calculated as a sum of the HF energy, the electron correlation MP2 contribution and zero-point vibrational energy. Fully optimized geometries of the syn and anti conformers of the compounds were determined, and the ionization energies of the above-mentioned acids were computed and the effects of the oxygen-by-sulfur and carbon-by-silicon substitution analysed. The calculations predict the syn forms always to be more stable. The highest gas-phase acidity (1513.9 kJ mol–1) has been calculated for carbamic acid. The replacement of the carbon and/or oxygen atoms of the carbamic acid in the substituted sila and thio derivatives evokes a decrease in the acidity. Changes in the Mulliken gross atomic populations were examined with respect to their dependence on the configuration and thio- and sila-substitution of carbamic acid.

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Article type: Paper
DOI: 10.1039/FT9938902375
J. Chem. Soc., Faraday Trans., 1993,89, 2375-2379

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    Structure and acidity of carbamic acid, and its thio, dithio and sila dervatives

    M. Remko, K. R. Liedl and B. M. Rode, J. Chem. Soc., Faraday Trans., 1993, 89, 2375
    DOI: 10.1039/FT9938902375

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