ISSN:
0894-3230
Keywords:
Organic Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
,
Physics
Notes:
The intersecting-state model (ISM) has been applied to the study of hydride transfer reactions between variously substituted and elaborated pyridinium ions in solution. Chemical bond order is conserved along the reaction coordinate, with a transition state bond order of n≠ = 0·5. This supports the view that these reactions have essentially a synchronous nature and occur by thermal activation over an energy barrier. Tunnelling of H- is negligible because the effective mass for the solvated species is high. Reaction energy and kinetic isotope effects are well accounted for by the model. For reactions in the vapour phase, ISM and the tunnel effect theory show that tunnelling becomes the dominant mechanism. The same is also valid for proton transfers in the vapour phase.
Additional Material:
5 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/poc.610030509
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