A Study of Reactive Intermediates Generated by One-Electron Transfers (Diazoalkane, Cieel, Chemiluminescence, Carbene, Peroxide)

Part I. 1-Phenyl-2-mesityl diazoethane, 1 is a unique example of a diazoalkane whose oxidative and non-oxidative decompositions are clearly distinguishable from the formation of mutually exclusive sets of products. In the thermolysis of photolysis of 1, steric hindrance provided by the mesityl group prevents bimolecular reactions while the 1,2-migrations normally observed for diazoethanes remain facile, giving only stable monomeric olefins as decomposition products. In the diazoalkane radical cation, 1('+), formed by chemical or elecro- chemical oxidation of 1, these migrations do not compete with fast bimolecular reactions. Reaction between 1('+) and neutral 1 gives the corresponding ketazine in a catalytic process. The principle fate of 1('+), however, is radical cation dimerization, giving stoichiometric amounts of stable, dehydrodimeric products by loss of two protons and two nitrogen molecules from the initially formed dication. No evidence was found to support the intermediacy of a carbene radical cation in these reactions. Electro-transfer quenching of the excited singlet state of 1,4-dicyanonaphthalene (DCN) by 1 was found by nanosecond transient absorption spectroscopy to generate DCN('-) and another short-lived species whose (lamda)(,max) occurs at ca. 520 nm. This absorption is tentatively assigned to 1('+).

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Illinois at Urbana-Champaign

Year dc:date

2014

Author dc:creator

• Little, Charles Bernard

• Chemistry, Organic

Identifier

(UMI)AAI8623357

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/70329