An Liu

Date of Graduation

1999

Document Type

Dissertation/Thesis

Abstract

The oxidation of d,l-1,2-bis(4-cyanophenyl)-1,2-ethanediol by ferriin (i.e., Fe(III)(1,10-phenanthroline)3 has been investigated. In contrast to the oxidation of other 1,2-diaryl-1,2-ethanediols, the presence of a pyridine base is required. Careful investigation of the kinetic behavior of this system reveals non-isosbestic point behavior. A complex mechanism is proposed to account for this oxidation reaction. This mechanism is in contrast to the normally observed outer-sphere electron pathway oxidation mechanisms of ferriin.1 The rates of ferriin oxidation of cis - and trans-1,2-diphenyl-1,2-cyclohexanediol have been found to be dramatically different. Cis-1,2-diphenyl-1,2-cyclohexanediol reacts a minimum of 104 times faster than the corresponding trans-isomer.2 Implications for the oxidation of benzylic diols by ferriin are discussed. 1This work is contained within a manuscript titled “Ferriin Oxidation of d,I-1,2-bis(4-cyanophenyl)-1,2-ethanediol: A Non-outer Sphere Electron Transfer Oxidation by Ferriin” which as been submitted to the Journal of Organic Chemistry. 2This work is contained within a manuscript titled “Geometric Requirements in the Ferriin Oxidation of Benzylic 1,2-Diols” has been submitted to the Journal of Chemical Society, Chemical Communication.

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