Wamser, Carl C. (1970) I. Photochemical studies of phenoxy radical. II. The photorecation of Michler's ketone with benzophenone. Dissertation (Ph.D.), California Institute of Technology. http://resolver.caltech.edu/CaltechETD:etd-02272009-093235
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I. Photochemical studies of phenoxy radical: Phenoxy radical was generated by flash photolysis of aqueous phenol. The ultraviolet-visible absorption spectrum of phenoxy radical was obtained. Decay kinetics for the bimolecular disappearance of phenoxy radical led to a second order rate constant of k[...] = 1.2 ± 0.1 x [...] sec[...]. In these solution-phase flash photolysis studies, no evidence was obtained for further decomposition of phenoxy radical. Molecular orbital symmetry correlations demonstrate that the conversion of phenoxy radical to cyclopentadienyl radical and carbon monoxide is symmetry-allowed from the ground state and symmetry-forbidden from the excited state of phenoxy radical.
II. The photorecation of Michler's ketone with benzophenone: Michler's ketone (4,4'-bis[dimethylamino]benzophenone) undergoes a photoreaction with benzophenone in 2-propanol to give photoproduct I with moderate quantum efficiency. This product arises from the coupling of benzophenone [...] ketyl radical with the corresponding radical derived from Michler's ketone. Each of these photointermediates was characterized by the absorption spectra and decay kinetics obtained from flash photolysis studies. The key mechanistic step must be transfer of hydrogen from the triplet state of Michler's ketone to benzophenone, and is without precedent in photochemistry. A triplet "exciplex" is postulated to lead to the hydrogen transfer.
|Item Type:||Thesis (Dissertation (Ph.D.))|
|Degree Grantor:||California Institute of Technology|
|Division:||Chemistry and Chemical Engineering|
|Thesis Availability:||Restricted to Caltech community only|
|Defense Date:||2 September 1969|
|Default Usage Policy:||No commercial reproduction, distribution, display or performance rights in this work are provided.|
|Deposited By:||Imported from ETD-db|
|Deposited On:||06 Mar 2009|
|Last Modified:||26 Dec 2012 02:32|
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