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Abstract: Iron, copper, and cobalt metal complexes of the pyridine-aza macrocyclic (PyMac) ligand, CRH's propionic acid-functionalized derivatives (deemed MLCOOH) were synthesized, characterized via X-Ray crystallography and various spectroscopic techniques, and assessed for their olefin epoxidation and phenol/catechol oxidation capabilities. The various metal complexes exhibited a tradeoff between ... read morestability and reactivity, wherein FeLCOOH was an effective olefin epoxidation catalyst but susceptible to decomposition. CuLCOOH was inactive in all oxidative reactions assessed, but robust. And CoLCOOH exhibited no olefin epoxidation capacity, but readily catalyzed the oxidation of 3,5-ditertbutylcatechol (3,5-DTBC) to 3,5-ditertbutylquinone (3,5-DTBQ). Spectrophotometric titration data show that the CuLCOOH and CoLCOOH complexes are isolated in their fully protonated states, rendering them amenable to structural characterization; whereas FeLCOO(H) was mostly deprotonated at first but could be eventually isolated in its acidic form.
Thesis (Ph.D.)--Tufts University, 2018.
Submitted to the Dept. of Chemistry.
Advisor: Sergiy Kryatov.
Committee: Terry Haas, Robert Stolow, and Jonathan Rochford.
Keyword: Inorganic chemistry.read less