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Date Permissions Signed

5-4-2021

Date of Award

Spring 2021

Document Type

Masters Thesis

Degree Name

Master of Science (MS)

Department

Chemistry

First Advisor

Gilbertson, John D.

Second Advisor

Scheuermann, Margaret Louise

Third Advisor

Kowalczyk, Tim

Abstract

Primary and secondary coordination sphere interactions with proximal Brønsted-Lowry acid/base sites were investigated using a family of pyridinediimine (PDI) complexes. The PDI ligands used in this project could be easily prepared by the Schiff base reactions with commercially available diamines as proton relays. Upon activation, the pendant Bronsted site and accessible electrons were arranged in a single scaffold that allowed the transportation of both protons and electrons to occur.

Two new PDI complexes with morpholine and pyrrolidine derivatives were introduced to the pendant PDI family. Their proton dissociation constant in acetonitrile were 17.1 and 18.3, respectively. The PDI complexes were subjected to reactions with nitrite and monitored via UV-Vis and IR spectroscopy, in which they exhibited much faster initial rates than some of the previously reported pendant PDI complexes. The rate enhancement effect was clearly evidenced by the stability of the corresponding mononitrosyl iron complex (MNIC) intermediate. These results had not yet been observed in other mononuclear PDI complexes and was attributed to the unique combination of proton responsivity, redox-activity and hemilability in the new pendant PDI systems.

Type

Text

Keywords

MNIC, mononitrosyl iron complex, hemilability, pyridinediimine

Publisher

Western Washington University

OCLC Number

1255889249

Subject – LCSH

Pyridine; Ligands; Morpholine; Pyrrolidine--Derivatives

Format

application/pdf

Genre/Form

masters theses

Language

English

Rights

Copying of this document in whole or in part is allowable only for scholarly purposes. It is understood, however, that any copying or publication of this document for commercial purposes, or for financial gain, shall not be allowed without the author’s written permission.

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