City Research Online

Abstract

The reactions in solution between tetracyanoethylene and the electron donating compounds, norbornadiene, hexamethy1 Dewar benzene and indole and between maleic anhydride and the compounds anthracene, methoxy-butadiene and hexadiene have been studied. The equilibrium constants, enthalpies’and entropies of formation and extinction coefficients of the charge-transfer complexes formed in reaction have been determined using the Benesi-Hildebrand method or using equimolar concentration of reactants.

The kinetics of reaction have been investigated using visible and ultraviolet spectroscopy having equimolar, excess of donor or, in one case, excess of acceptor concentrations of reactants. For each reaction the kinetic data has been used to examine the overall mechanism of reaction with particular reference to the role that the charge-transfer complex might play as a reaction intermediate; only in the cage of the reactions of norbornadiene and hexamethyl Dewar benzene was a charge-transfer complex indicated as a likely reaction intermediate. The structures of the products of reaction were determined using elemental analysis, mass spectrometry, infrared and nuclear magnetic resonance spectroscopy.

The conformations in solution of these and other closely related adducts were examined using nuclear magnetic resonance spectroscopy with application of the Karplus equation.

Publication Type:	Thesis (Doctoral)
Subjects:	Q Science > QD Chemistry
Departments:	School of Science & Technology > School of Science & Technology Doctoral Theses Doctoral Theses

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