Abstract
Effects of pressure on thermal Z/E isomerization of substituted N-benzylideneanilines and azobenzenes were studied in 2-methyl-2,4-pentanediol. Pressure dependence of the Z/E isomerization of a substituted azonaphthalene was also studied in glycerol triacetate. From the results in this and earlier papers, the following conclusions were reached. 1) It is possible to cast slow thermal reactions into the state of fluctuation control in highly viscous liquid phase realized by a combination of a viscous liquid and high pressure. 2) The viscosity dependence of the rate constant can be rationalized by the two-dimensional reaction-coordinate model developed by Sumi but not by the Grote-Hynes' theory of frequency-dependent friction. Namely, the energy-barrier crossing takes place after the solvent molecules are rearranged to accommodate the transition state. 3) Whether the solvent rearrangement involves chemical transformations with appreciable energy increases depends on the nature of the reaction and the solvent.
| Original language | English |
|---|---|
| Pages (from-to) | 551-560 |
| Number of pages | 10 |
| Journal | Bulletin of the Chemical Society of Japan |
| Volume | 69 |
| Issue number | 3 |
| DOIs | |
| Publication status | Published - Jan 1 1996 |
| Externally published | Yes |
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All Science Journal Classification (ASJC) codes
- Chemistry(all)
Cite this
Effects of Solvent Fluctuations on the Rate of Thermal Z/E Isomerization of Azobenzenes and N-Benzylideneanilines. / Asano, Tsutomu; Cosstick, Kevin; Furuta, Hiroyuki; Matsuo, Kohei; Sumi, Hitoshi.
In: Bulletin of the Chemical Society of Japan, Vol. 69, No. 3, 01.01.1996, p. 551-560.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Effects of Solvent Fluctuations on the Rate of Thermal Z/E Isomerization of Azobenzenes and N-Benzylideneanilines
AU - Asano, Tsutomu
AU - Cosstick, Kevin
AU - Furuta, Hiroyuki
AU - Matsuo, Kohei
AU - Sumi, Hitoshi
PY - 1996/1/1
Y1 - 1996/1/1
N2 - Effects of pressure on thermal Z/E isomerization of substituted N-benzylideneanilines and azobenzenes were studied in 2-methyl-2,4-pentanediol. Pressure dependence of the Z/E isomerization of a substituted azonaphthalene was also studied in glycerol triacetate. From the results in this and earlier papers, the following conclusions were reached. 1) It is possible to cast slow thermal reactions into the state of fluctuation control in highly viscous liquid phase realized by a combination of a viscous liquid and high pressure. 2) The viscosity dependence of the rate constant can be rationalized by the two-dimensional reaction-coordinate model developed by Sumi but not by the Grote-Hynes' theory of frequency-dependent friction. Namely, the energy-barrier crossing takes place after the solvent molecules are rearranged to accommodate the transition state. 3) Whether the solvent rearrangement involves chemical transformations with appreciable energy increases depends on the nature of the reaction and the solvent.
AB - Effects of pressure on thermal Z/E isomerization of substituted N-benzylideneanilines and azobenzenes were studied in 2-methyl-2,4-pentanediol. Pressure dependence of the Z/E isomerization of a substituted azonaphthalene was also studied in glycerol triacetate. From the results in this and earlier papers, the following conclusions were reached. 1) It is possible to cast slow thermal reactions into the state of fluctuation control in highly viscous liquid phase realized by a combination of a viscous liquid and high pressure. 2) The viscosity dependence of the rate constant can be rationalized by the two-dimensional reaction-coordinate model developed by Sumi but not by the Grote-Hynes' theory of frequency-dependent friction. Namely, the energy-barrier crossing takes place after the solvent molecules are rearranged to accommodate the transition state. 3) Whether the solvent rearrangement involves chemical transformations with appreciable energy increases depends on the nature of the reaction and the solvent.
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U2 - 10.1246/bcsj.69.551
DO - 10.1246/bcsj.69.551
M3 - Article
VL - 69
SP - 551
EP - 560
JO - Bulletin of the Chemical Society of Japan
JF - Bulletin of the Chemical Society of Japan
SN - 0009-2673
IS - 3
ER -