Computational study of the cooperative effects of nitrogen and silicon atoms on the singlet-triplet energy spacing in 1,3-diradicals and the reactivity of their singlet states

Takeshi Nakamura, Laura Gagliardi, Manabu Abe

Research output: Contribution to journalReview articlepeer-review

21 Scopus citations

Abstract

Quantumchemical calculationswere performed to investigate the cooperative effect of the nitrogen and silicon atoms on the singlet-triplet energy spacing and the reactivity of the singlet state in 1,2-diazacyclopentane-3,5-diyls and 1,2-diaza-4-silacyclopentane-3,5-diyls. The largest singlet-triplet energy gap (DEc ST 1/4 S36.1 kcal/mol) found so far in localized 1,3-diradicals was in the C2v symmetry of 4,4-difluoro-1,2-diaza-4-silacyclopentane-3,5-diyl atthe UB3LYP/ 6-31G(d) level of theory. The cooperative effect was also found in the energy differences of singlet diradicals with the corresponding ring-closing compounds, bicyclo[2.1.0]pentane derivatives. The singlet state of the 1,2-diaza-4-silacyclopentane-3,5-diyls was calculated to be energeticallymore stable than the ring-closing compound. The notable finding on the stability of the singlet diradicalsmay be attributed to the resonance structures that specifically stabilize the singlet state of diradicals. The computational studies predict that the singlet 1,2-diaza-4-silacyclopentane-3,5-diyl is a persistent molecule under conditions without intermolecular-trapping reagents.

Original languageEnglish (US)
Pages (from-to)300-307
Number of pages8
JournalJournal of Physical Organic Chemistry
Volume23
Issue number4
DOIs
StatePublished - Apr 2010

Keywords

  • Cooperative effect
  • Heteroatom effect
  • Homolytic reactions
  • Nitrogen-atom effect
  • Quantum chemical calculations
  • Silicon-atom effect
  • Singlet diradicals
  • Substituent effect

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