A computational study on the stability of diaminocarbenes

Mu Jeng Cheng, Ching-Han Hu

Research output: Contribution to journalArticle

32 Citations (Scopus)

Abstract

The 1,2-H shift, 1,2-Me shift, and dimerization reactions of several diaminocarbenes have been studied using density functional theory and ab initio methods. It was observed that the activation energies (Ea) for the dimerization of diaminocarbenes are much smaller than those of 1,2-H shift, 1,2-Me shift and insertion. Dimerization is thus the most likely course of reaction for diaminocarbenes. The activation energies for the dimerization of diaminocarbenes which exhibit 6π-electron delocalization are larger than those of the non-aromatic ones. For cyclic diaminocarbenes there is a proportional relation between Ea and the singlet-triplet gap (ΔES-T), i.e., Ea of dimerization is larger as ΔES-T increases.

Original languageEnglish
Pages (from-to)83-90
Number of pages8
JournalChemical Physics Letters
Volume322
Issue number1-2
DOIs
Publication statusPublished - 2000 May 12

Fingerprint

Dimerization
dimerization
shift
Activation energy
activation energy
Density functional theory
insertion
density functional theory
Electrons
electrons

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

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abstract = "The 1,2-H shift, 1,2-Me shift, and dimerization reactions of several diaminocarbenes have been studied using density functional theory and ab initio methods. It was observed that the activation energies (Ea) for the dimerization of diaminocarbenes are much smaller than those of 1,2-H shift, 1,2-Me shift and insertion. Dimerization is thus the most likely course of reaction for diaminocarbenes. The activation energies for the dimerization of diaminocarbenes which exhibit 6π-electron delocalization are larger than those of the non-aromatic ones. For cyclic diaminocarbenes there is a proportional relation between Ea and the singlet-triplet gap (ΔES-T), i.e., Ea of dimerization is larger as ΔES-T increases.",
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A computational study on the stability of diaminocarbenes. / Cheng, Mu Jeng; Hu, Ching-Han.

In: Chemical Physics Letters, Vol. 322, No. 1-2, 12.05.2000, p. 83-90.

Research output: Contribution to journalArticle

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