Dissertation/Thesis Abstract

Electrochemical and Spectroelectrochemical Investigations into Derivatives of Ruthenium Nitrosyl Schiff Base and Porphyrin Complexes
by Ramuglia, Anthony, M.S., Southern Illinois University at Edwardsville, 2018, 109; 13420342
Abstract (Summary)

The synthesis, characterization and cathodic electrochemistry of [Ru(salen)(NO)(Cl)], and [Ru(saloph)(NO)(Cl)] was conducted. Both complexes exhibit electrochemical wave shapes indicative of a chemical step which takes place after one-electron reduction. The chemical mechanism for both species is proposed as a chloride-for-solvent metathesis, as the addition of an external chloride source influences wave shape reversibility. The kinetic and thermodynamic parameters of the singly reduced [Ru(salen)(NO)(Cl)] were calculated through digital simulations to elucidate the rate of chloride loss from the complex. Infrared spectroelectrochemistry was performed on the [Ru(salen)(NO)(Cl)] species in an effort to gain insight into structural changes within the molecule after reduction. A new method which uses CsPF6 and deuterated acetonitrile (CD3CN) has allowed for a more complete electrochemical characterization technique. This technique has allowed for the observation of a wider frequency window within the infrared region, which allows for the direct observation of NO stretching frequencies of singly and doubly reduced complexes. Upon addition of proton sources, an IR bands consistent with the generation of coordinated HNO compound is observed.

The anodic electrochemistry, IR and EPR spectroelectrochemistry was conducted on a series of [Ru(OEP)(NO)(phenolate)] complexes synthesized by Jeremy Zink, Dr. Erwin Abucayon, and Dr. Adam Warhausen at the University of Oklahoma. These species were observed to undergo a chemical mechanism after oxidation due to changes in CV wave shape with scan rate. Digital simulations in conjunction with IR and EPR spectroelectrochemistry suggest that the initial one-electron oxidation is a ligand-centered process, and results in a ligand-based radical on the OR component. The differences in ligand stability once oxidized results in either dimerization between two Ru complexes through the ligand as in Ru(OEP)(NO)(OPh) or ligand dissociation followed by dimerization as in Ru(OEP)(NO)( 1HL) and Ru(OEP)(NO)(2HL) where (1HL) = (C6H3-(2-NHC(=O)CF3)) and (2HL) = (C6H3-(2,6-NHC(=O)CF3)2)

Indexing (document details)
Advisor: Shaw, Michael J.
Commitee: Jones, Myron, Navarre, Edward
School: Southern Illinois University at Edwardsville
Department: Chemistry
School Location: United States -- Illinois
Source: MAI 58/04M(E), Masters Abstracts International
Subjects: Chemistry
Publication Number: 13420342
ISBN: 978-0-438-82399-0
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