Details
| Original language | English |
|---|---|
| Pages (from-to) | 3339-3342 |
| Number of pages | 4 |
| Journal | ChemPhysChem |
| Volume | 11 |
| Issue number | 15 |
| Early online date | 6 Sept 2010 |
| Publication status | Published - 25 Oct 2010 |
Abstract
In first-principles molecular dynamics simulations of the mechanically induced ring-opening of substituted benzocyclobutene we observe both con- and disrotatory ring-opening reactions. We show that this finding does not contradict the fundamental principle that the orbitals develop continuously in time. However, it constitutes an exception from the principle of the conservation of orbital symmetry and thus is indeed an exception from the Woodward-Hoffmann rules. In contrast, the ring-opening of unsubstituted cyclobutene proceeds in a conrotatory fashion. This shows that the breaking of the Woodward-Hoffmann rules is significantly facilitated by the substituents.Limits of control: Exposing functionalized benzocyclobutene to mechanical load may lead to both con- and disrotatory ring-opening reactions (see figure). Using Car-Parrinello molecular dynamics simulations it is shown that the thermally forbidden process is related to a localisation of the frontier orbitals.
Keywords
- Car-Parrinello molecular dynamics, Density functional calculations, Reaction mechanisms, Ring-opening reactions, Woodward-Hoffmann rules
ASJC Scopus subject areas
- Physics and Astronomy(all)
- Atomic and Molecular Physics, and Optics
- Chemistry(all)
- Physical and Theoretical Chemistry
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In: ChemPhysChem, Vol. 11, No. 15, 25.10.2010, p. 3339-3342.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - Conservation of Orbital Symmetry can be Circumvented in Mechanically Induced Reactions
AU - Friedrichs, Jana
AU - Lüßmann, Mathias
AU - Frank, Irmgard
PY - 2010/10/25
Y1 - 2010/10/25
N2 - In first-principles molecular dynamics simulations of the mechanically induced ring-opening of substituted benzocyclobutene we observe both con- and disrotatory ring-opening reactions. We show that this finding does not contradict the fundamental principle that the orbitals develop continuously in time. However, it constitutes an exception from the principle of the conservation of orbital symmetry and thus is indeed an exception from the Woodward-Hoffmann rules. In contrast, the ring-opening of unsubstituted cyclobutene proceeds in a conrotatory fashion. This shows that the breaking of the Woodward-Hoffmann rules is significantly facilitated by the substituents.Limits of control: Exposing functionalized benzocyclobutene to mechanical load may lead to both con- and disrotatory ring-opening reactions (see figure). Using Car-Parrinello molecular dynamics simulations it is shown that the thermally forbidden process is related to a localisation of the frontier orbitals.
AB - In first-principles molecular dynamics simulations of the mechanically induced ring-opening of substituted benzocyclobutene we observe both con- and disrotatory ring-opening reactions. We show that this finding does not contradict the fundamental principle that the orbitals develop continuously in time. However, it constitutes an exception from the principle of the conservation of orbital symmetry and thus is indeed an exception from the Woodward-Hoffmann rules. In contrast, the ring-opening of unsubstituted cyclobutene proceeds in a conrotatory fashion. This shows that the breaking of the Woodward-Hoffmann rules is significantly facilitated by the substituents.Limits of control: Exposing functionalized benzocyclobutene to mechanical load may lead to both con- and disrotatory ring-opening reactions (see figure). Using Car-Parrinello molecular dynamics simulations it is shown that the thermally forbidden process is related to a localisation of the frontier orbitals.
KW - Car-Parrinello molecular dynamics
KW - Density functional calculations
KW - Reaction mechanisms
KW - Ring-opening reactions
KW - Woodward-Hoffmann rules
UR - http://www.scopus.com/inward/record.url?scp=77958539618&partnerID=8YFLogxK
U2 - 10.1002/cphc.201000460
DO - 10.1002/cphc.201000460
M3 - Article
AN - SCOPUS:77958539618
VL - 11
SP - 3339
EP - 3342
JO - ChemPhysChem
JF - ChemPhysChem
SN - 1439-4235
IS - 15
ER -