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Kinetic Studies of Hydrogen Oxidation by Cobaloximes and Synthesis, Spectroscopy and Boronation of a New Heteroleptic Ruthenium Cyanide Complex

Citation

Del Ciello, Sarah Anne (2020) Kinetic Studies of Hydrogen Oxidation by Cobaloximes and Synthesis, Spectroscopy and Boronation of a New Heteroleptic Ruthenium Cyanide Complex. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/6QTC-G360. https://resolver.caltech.edu/CaltechTHESIS:11152019-095230239

Abstract

Cobaloximes are macrocyclic complexes well-studied as homogeneous catalysts for hydrogen evolution, but they are also competent at the microscopic reverse reaction, hydrogen oxidation. Kinetic studies of Co(dmgBF2)2L2 reacting with hydrogen and base reveal a rate law that is second-order in cobalt and first-order in H2, indicating that the mechanism of H-H bond breaking is homolytic.

The reduction potentials of metal cyanide complexes can be tuned by appending boranes to the N-terminus. By boronating ruthenium cyanide complexes containing diimine ligands, the RuII/III couple can be tuned without drastic modification of the diimine0/- couple. A new member of the [Ru(dimmine)(CN)4]2- family is synthesized with the ligand 4,4’-bis(trifluoromethyl)-2,2’-bipyridine (CF3bpy) and boronated, resulting in a molecule with two reversible redox events separated by 3.2 V.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:hydrogen, cobaloximes, boranes, cobalt, ruthenium, cyanide, bipyridine
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Gray, Harry B.
Thesis Committee:
  • Reisman, Sarah E. (chair)
  • Gray, Harry B.
  • Peters, Jonas C.
  • See, Kimberly
Defense Date:22 November 2019
Funders:
Funding AgencyGrant Number
National Science Foundation (NSF)CHE-1305124
National Science Foundation (NSF)CHE-1763429
Record Number:CaltechTHESIS:11152019-095230239
Persistent URL:https://resolver.caltech.edu/CaltechTHESIS:11152019-095230239
DOI:10.7907/6QTC-G360
ORCID:
AuthorORCID
Del Ciello, Sarah Anne0000-0002-7571-8944
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:13577
Collection:CaltechTHESIS
Deposited By: Sarah Del Ciello
Deposited On:20 Dec 2019 17:59
Last Modified:21 Dec 2020 21:36

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