ISSN:
0538-8066
Schlagwort(e):
Chemistry
;
Physical Chemistry
Quelle:
Wiley InterScience Backfile Collection 1832-2000
Thema:
Chemie und Pharmazie
Notizen:
Time-resolved absorption spectra for a reaction mixture of p-methoxystyrene and tetracyanoethylene (TCNE) are found to have a band maximum at 325 nm which is assigned to the 1,4-cycloadduct. The reaction in chloroform at 15, 20, and 25°C is followed by the charge-transfer band at 600 nm. The 1,4-cycloadduct, besides the so far known 1,2-cycloadduct and EDA complex, is taken into account to derive the rate equation for the EDA complex that is a linear second-order differential equation. The rate constants for the elementary steps involved in the reaction are obtained. The 1,4-cycloaddition has an activation entropy of -63 J/K·mol for the cycloreversion and a reaction constant ρ of -4.7, both of which indicate the polar transition state. On the other hand, activation entropy of the 1,2-cycloaddition is 73 J/K·mol more negative than that of the 1,4-cycloaddition, supporting the zwitterionic mechanism for the 1,2-cycloaddition.
Zusätzliches Material:
5 Ill.
Materialart:
Digitale Medien
URL:
http://dx.doi.org/10.1002/kin.550140904
