Topic
Molozonide
About: Molozonide is a research topic. Over the lifetime, 16 publications have been published within this topic receiving 210 citations.
Papers
TL;DR: In this paper, a series of diene polymers with unconjugated double bonds is considered and it is shown that the reaction rate with ozone (in solution) correlates with the free energy of reaction of each molozonide calculated according to MM + and AM 1 methods.
64 citations
TL;DR: Though the direct dynamics simulations are classical, better agreement is obtained using quantum instead of classical harmonic RRKM theory, and correlations are found between the stretching motions of molozonide, indicative of nonchaotic and non-RRKM dynamics.
Abstract: A direct chemical dynamics simulation, at the B3LYP∕6-31G(d) level of theory, was used to study the post-transition state intramolecular and unimolecular dynamics for the O3+propene reaction. Comparisons of B3LYP∕6-31G(d) with CCSD(T)/cc-pVTZ and other levels of theory show that the former gives accurate structures and energies for the reaction’s stationary points. The direct dynamics simulations are initiated at the anti and syn O3+propene transition states (TSs) and the TS symmetries are preserved in forming the molozonide intermediates. Anti↔syn molozonide isomerization has a very low barrier of 2–3kcal∕mol and its Rice-Ramsperger-Kassel-Marcus (RRKM) lifetime is 0.3ps. However, the trajectory isomerization is slower and it is unclear whether this anti↔syn equilibration is complete when the trajectories are terminated at 1.6ps. The syn (anti) molozonides dissociate to CH3CHO+H2COO and H2CO+syn (anti) CH3CHOO. The kinetics for the latter reactions are in overall good agreement with RRKM theory, but ther...
63 citations
TL;DR: In this article, the authors showed that the equatorial belt of 15 hexagons of C70, with its relatively high π density may explain the slower rate of ozonation of C 70.
Abstract: C60, C70, C76, C78, and C84 dissolved in toluene, were treated at 23.5°C with ozone. The concentrations of all five fullerenes decreased with increasing dose of ozone, but C60, C76, C78, and C84 transformed significantly faster than C70. Oxides of C60 and C70, but not of the other fullerenes, were observed in the ozonated solutions. We assume that all five fullerenes form molozonides, which swiftly lose molecular oxygen to form oxides. We assume further that the molozonide always forms at an interpentagonal bond. The π-bond orders calculated by Taylor for such bonds may explain the faster ozonation of C76, C78, and C84, but probably not of C60. We suggest that the “equatorial belt” of 15 hexagons of C70, with its relatively high π density may be the cause for the slower rate of ozonation of C70.
28 citations
TL;DR: The photochemical cycloaddition of nitrobenzene to cyclohexene at −70 °C gives an unstable crystalline adduct, an analogue of a molozonide, which has been characterized as discussed by the authors.
Abstract: The photochemical cycloaddition of nitrobenzene to cyclohexene at −70 °C gives an unstable crystalline adduct, an analogue of a molozonide, which has been characterized. Similar results have been o...
21 citations
21 citations
Related Topics (5)
Performance Metrics
| Year | Papers |
|---|---|
| 2014 | 1 |
| 2008 | 1 |
| 2006 | 1 |
| 2002 | 1 |
| 2001 | 1 |
| 1993 | 1 |