Date of Graduation
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 â€œFerriin Oxidation of d,I-1,2-bis(4-cyanophenyl)-1,2-ethanediol: A Non-outer Sphere Electron Transfer Oxidation by Ferriinâ€ which as been submitted to the Journal of Organic Chemistry. 2This work is contained within a manuscript titled â€œGeometric Requirements in the Ferriin Oxidation of Benzylic 1,2-Diolsâ€ has been submitted to the Journal of Chemical Society, Chemical Communication.
Liu, An, "Ferriin oxidation of benzylic 1,2 -diols: A mechanistic approach." (1999). Graduate Theses, Dissertations, and Problem Reports. 9314.