Title page for ETD etd-102498-111245

Type of Document Dissertation
Author Phillips, Janice Paige
URN etd-102498-111245
Title Rearrangements of Radical Anions Generated from Cyclopropyl Ketones
Degree PhD
Department Chemistry
Advisory Committee
Advisor Name Title
Tanko, James M. Committee Chair
Anderson, Mark R. Committee Member
Brewer, Karen J. Committee Member
Castagnoli, Neal Jr. Committee Member
Gibson, Harry W. Committee Member
Wolfe, James F. Committee Member
  • Marcus theory
  • Homogeneous catalysis
  • Reaction mechanism and kinetics
  • Cyclopropyl ketones
  • Voltammetry
  • Cathodic reduction
  • Ring opening
  • Radical anion
Date of Defense 1998-05-04
Availability restricted
Cyclopropyl-containing substrates have been

frequently utilized as "probes" for the detection

of SET pathways in organic and biorganic systems.

These reactions are based on the

cyclorpropylcarbinyl - homoallyl rearrangement,

which is fast and essentially irreversible.

The implicit assumption in such studies is that if

a "radical" species is produced, it will undergo

ring opening. We have found that there are two

important factors to consider in the design of

SET probes: 1) ring strain, the thermodynamic

driving force for the rearrangement, and

2) resonance energy, which may help or hinder

rearrangement, depending on the specific system.

Delocalization of spin and charge were found to

be important factors pertaining to substituent

effects on the rates of radical anion


Previous studies from our lab have

centered on highly conjugated phenyl

cyclopropyl ketones. This work considers a series

of compounds varying in their conjugative

components from a highly conjugated

spiro[2.5]octa-4,7-dien-6-one and derivatives to

simple aliphatic ketones. Utilizing cyclic,

linear sweep voltammetry, and preparative

electrolysis techniques, it was discovered that

all substrates yielded ring opened products with

rates and selectivities that will prove useful

and informative in the design of mechanistic

probes based on the cyclorpropylcarbinyl -

homoallyl rearrangement. Rates of homogeneous

electron transfer from a series of hydrocarbon

mediators to substrates were measured using

homogeneous catalysis techniques. Standard

reduction potentials and reorganization energies

of substrates were derived using Marcus theory.

Conjugative interactions with the cyclopropyl

group are discussed.

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