Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Comparative Studies on the Reactions of Carbamyl and Thiocarbamyl Halides with NH3 in the Gas Phase and in Aqueous Solution: A Theoretical Study

  • Kim, Chang-Kon (Department of Chemistry, Inha University) ;
  • Han, In-Suk (Department of Chemistry, Inha University) ;
  • Sohn, Chang-Kook (Department of Chemistry Education, Chonnam National University) ;
  • Yu, Yu-Hee (Department of Chemistry Education, Chonnam National University) ;
  • Su, Zhishan (Department of Chemistry, Inha University) ;
  • Kim, Chan-Kyung (Department of Chemistry, Inha University)
  • Received : 2012.02.23
  • Accepted : 2012.03.14
  • Published : 2012.06.20
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Abstract

In this work, the reactions of carbamyl and thiocarbamyl halides with $NH_3$ were studied in the gas phase at the MP2(FC)/6-31+G(d) level of theory. Single point calculations were performed at the QCISD/6-311+G(3df,2p) to refine the energetics. The reaction mechanisms were also studied in aqueous solution. The structures were fully optimized at the CPCM-MP2(FC)/6-31+G(d) and refined by a single point CPCM-QCISD/6-311+G(3df,2p) calculations. The reaction mechanisms for the title compounds were compared with those for the acetyl and thioacetyl halides. The lower reactivity of carbamyl (and thiocarbamyl) groups was explained by comparing the C=O and C=S ${\pi}$-bond strengths as well as resonance contributions in the ground state.

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References

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