The effect of fluorination on the surface chemistry of adsorbate-metal systems

Ultra-high vacuum surface techniques are used to determine the effect of substituents (mainly fluorine) on the surface chemistry of several adsorbate-metal systems. In the first system, the effect of two substituent groups ($-$CH$\sb3$ and $-$F) on the kinetics of the phenyl coupling reaction on the Cu(111) surface has been studied. The electron withdrawing fluorine group in the meta or para position of the phenyl ring was shown to lower the activation barrier to phenyl coupling while fluorine in the ortho position raised the barrier. The electron donating methyl group in the meta position was found to raise the activation barrier. From the activation barriers and preexponentials, reaction rate constants were calculated and used to construct a linear free energy relationship or Hammett plot. From this plot the reaction constant was found to be $6.0\pm3.3.$ The positive value of the reaction constant indicates that the transition state of the phenyl coupling reaction is electron rich with respect to the initial state.

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

2011

Author dc:creator

• Meyers, Jerry Michael

Contributors dc:contributor

• Gellman, A.J.

• Chemistry, Physical

Statement dc:rights

• Copyright 1995 Meyers, Jerry Michael

Language dc:language

eng

Identifier

AAI9624438
(UMI)AAI9624438

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/22821