Isomerization reactions of RSNO (R=H, CnH2n+1 n ≤ 4)

Chin Hung Lai*, Elise Y. Li, Pi Tai Chou

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

15 Citations (Scopus)


We have applied various theoretical methods to gain detailed insights into the isomers as well as the transition states (TSs) along the corresponding reaction pathways for RSNO (R=H, CnH2n+1 n ≤ 4). On the basis of G2 and G2MP2 results, the relative order of stability for R=H is estimated to be trans-HSNO > cis-HSNO > HNSO > cis-HONS ≈ trans-HONS, while it is cis-CH3SNO ≈ trans-CH3SNO > CH3NSO > trans-CH3ONS > cis-CH3ONS for R=CH3. A similar trend is also obtained from the B3P86 method with considerably less computing effort if the nearly isoenergetic isomers cis-HONS and trans-HONS are ignored. Based on the results of B3P86, cis-RSNO is more stable than trans-RSNO when R=H is replaced by alkyl groups except for R=t-Bu. Natural bond orbital analyses allow us to explore whether the high reactivity of S-nitrosothiols is due to the strong negative hyperconjugation (n πO ↔ σ*N-S). The mesomeric effect of S-nitrosothiols, although non-negligible, does not cause the breakage of N-O bond due to the compensation of columbic attraction between N and O.

Original languageEnglish
Pages (from-to)145-152
Number of pages8
JournalTheoretical Chemistry Accounts
Issue number1
Publication statusPublished - 2007 Jan
Externally publishedYes


  • B3P86
  • G2
  • Mesomeric effect
  • Negative hyperconjugation
  • RSNO

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry


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