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Master of Science (MS)
Gilbertson, John D.
Rider, David A.
The activation of small molecules has been studied by the scientific field for many decades as it plays a key role in nature such as photosynthesis and respiration. Many of these reactions are catalyzed by metalloenzymes in nature where the transfer of electrons and protons are coupled for the reaction to move forward. Noncovalent interactions in the secondary coordination sphere of metalloenzymes play an important role in determining the activity and selectivity. Hydrogen bonds are the most common noncovalent interactions that metalloenzymes utilize to control the reactivity in the secondary coordination sphere. Therefore, it is important to develop compounds and catalysts that can move both protons and electrons. Recent studies have been done by several groups on the mechanism of nitrite reduction. Based on those findings, we developed a series of iron (II) pyridinediimine (PDI) complexes that contain pendant bases, with varying pKa values, located in the secondary coordination sphere. These ligands were synthesized, coordinated to iron (II) and reduced under carbon monoxide (CO) to store electrons within the ligand scaffold. These reduced complexes were then protonated to form hydrogen bonds and fine tune the reactivity. These PDI complexes that are capable of storing both electrons and protons were investigated to functionally mimic the metalloenzyme nitrite reductase. To date, the mechanism of nitrite reduction remains unknown. In an attempt to determine how nitrite binds to the metal of our PDI complex, we synthesized a dinitrosyl iron complex. The synthesis of this complex should help to determine the mechanism of nitrite reduction.
Western Washington University
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Kwon, Yubin, "Synthesis & Reactivity of Iron (II) Pyridinediimine Complexes For the Reduction of Nitrite" (2016). WWU Masters Thesis Collection. 474.