Tautomerism and mechanism of intramolecular proton transfer under the gas phase and micro-hydrated solvent conditions: biuret as a case study

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• 作者：Abdol Reza Hajipour ; Alireza Najafi Chermahini ; Morteza Karimzadeh…
• 关键词：Biuret ; Proton transfer ; DFT ; Solvent effect ; Microhydration
• 刊名：Structural Chemistry
• 出版年：2015
• 出版时间：February 2015
• 年：2015
• 卷：26
• 期：1
• 页码：159-169
• 全文大小：695 KB
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• 刊物类别：Chemistry and Materials Science
• 刊物主题：Chemistry
  Computer Applications in Chemistry
  Physical Chemistry
  Theoretical and Computational Chemistry
  
• 出版者：Springer Netherlands
• ISSN：1572-9001

文摘

The electronic structures, intramolecular proton transfers, and rotational barriers around C–N, O–H, and N–H bonds in the biuret isomers have been investigated at B3LYP/6-311+G(2d,p) level of theory. The results showed that biuret is nearly planar and the diketo form 1 involving hydrogen in the central nitrogen N6 and in a trans-conformation of amino group and carbonyl group is the most stable isomer. Furthermore, in the next step, conversion of five most stable isomers to each other was also investigated. The results indicated that intramolecular proton-transfer step is the rate-determining step in all paths. Study of the relative stabilities and mechanism of conversion of isomers have been performed with polarizable continuum model, and it was found that with going to polar solvents the order of stabilities did not change. The heights of barrier for PT mechanism assisted by one-water molecule was also studied and calculated results showed that the water molecule assisting PT has much lower energy barrier than analogous barrier in the gas phase. Moreover, NBO calculation is carried out for tautomers to obtain donor–acceptor interactions.