A Caltech Library Service

Mechanistic Study of Cu-Mediated, Photoinduced C–S Bond Formation and Demonstration of Electrochemical Ammonia Production by a Surface-Attached Iron Complex


Hannoun, Kareem Imad (2019) Mechanistic Study of Cu-Mediated, Photoinduced C–S Bond Formation and Demonstration of Electrochemical Ammonia Production by a Surface-Attached Iron Complex. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/R9EJ-KX83.


The worldwide reliance on fossil fuels for energy and petrochemicals poses a massive environmental hazard. Furthermore, many chemical processes rely on precious metals that have low abundance on Earth and are threatened. As the world population grows rapidly, these factors pose an increasing threat to our planet and new chemical processes are needed that employ earth-abundant catalysts and alternative chemical currencies such as light and electricity derived from renewable sources.

Chapter 2 discusses an in-depth mechanistic study of the photoinduced, copper-mediated cross-coupling of aryl thiols with aryl halides. This reaction employs light energy and an earth-abundant metal to achieve bond formation through a pathway distinct from that of thermal reactions. In particular, I focus on the stoichiometric photochemistry and subsequent reactivity of a [CuI(SAr)2] complex (Ar = 2,6-dimethylphenyl). A broad array of experimental techniques furnish data consistent with a pathway in which a photoexcited [CuI(SAr)2]-* complex undergoes SET to generate a CuII species and an aryl radical, which then couple through an in-cage radical recombination.

Chapter 3 discusses the surface attachment of a P3BFe complex to a carbon electrode, and the electrochemical generation of ammonia from N2 by the surface-appended species (P3BFe = tris-phosphinoborane). Ammonia production is achieved industrially by the combination of N2 and H2, the latter of which is derived from methane with concomitant production of CO2. Alternative chemical processes, such as the use of energy derived from electricity, are vital for the decreasing the carbon footprint of ammonia production. Synthetic modification of a previously-reported P3BFe complex by addition of three pyrene substituents onto the catalyst backbone allows non-covalent attachment onto a graphite surface. The resulting functionalized electrode shows good stability towards iron desorption under highly reducing conditions, and produces 1.4 equiv NH3 per iron site. The data presented provide the first demonstration of electrochemical nitrogen fixation by a molecular complex appended to an electrode.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:Nitrogen fixation, electrochemistry, photochemistry, ammonia, thiol, cross coupling
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Peters, Jonas C.
Thesis Committee:
  • Fu, Gregory C. (chair)
  • Agapie, Theodor
  • Miller, Thomas F.
  • Peters, Jonas C.
Defense Date:6 May 2019
Record Number:CaltechTHESIS:05302019-070503222
Persistent URL:
Related URLs:
URLURL TypeDescription adapted for Chapter 2.
Hannoun, Kareem Imad0000-0003-3176-1104
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:11565
Deposited By: Kareem Hannoun
Deposited On:31 May 2019 20:41
Last Modified:08 Nov 2023 00:44

Thesis Files

PDF (Full Thesis) - Final Version
See Usage Policy.

PDF (Chapter 1) - Final Version
See Usage Policy.

PDF (Chapter 2) - Final Version
See Usage Policy.

PDF (Chapter 3) - Final Version
See Usage Policy.

PDF (Appendix A) - Final Version
See Usage Policy.

PDF (Appendix B) - Final Version
See Usage Policy.


Repository Staff Only: item control page