Dissertation Information for Do Trong BaoNAME:
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SCHOOL: ADVISORS: COMMITTEE MEMBERS: MPACT Status: Fully Complete Title: Steric effects on the stability and reactivity of model complexes of non-heme diiron proteins and ferritin Abstract: "The effects of bulky ligands on the stability and reactivity of a series of ì-hydroxo bis(carboxylato) bridged diiron(II) complexes were investigated. The complexes [Fe2(ì-OH)(O 2 CR) 2 (Bn 3 tacn) 2 ]OTf (O 2 CR = p -F-PhCO 2 , p -CF 3 O-PhCO 2 or AdaCO 2 ; Bn 3 tacn = 1,4,7-tribenzyl-1,4,7-triazacyclononane) and [Fe 2 (ì-OH)(AdaCO 2 ) 2 (Me 3 tacn) 2 ]OTf (Me 3 tacn = 1,4,7-trimethyl-1,4,7-triazacyclononane) were synthesized and their X-ray crystal structures reported. NMR spectroscopic studies provide solution characterization, and the results correspond well with their solid state description. NMR results reveal the ligands to be kinetic labile at room temperature. The reactivity of these complexes toward dioxygen at room temperature was monitored over time by electronic absorption spectroscopy. The formation and decay of an absorbance maximum in the range 670-680 nm was observed for each complex. The lifetime (t max ) of the absorbance maxima varies and reflects the bulk properties of the respective complex. Their redox properties were explored using cyclic voltammetry. Results here revealed increasing stability of the mixed valence species with increasing bulk properties. The mixed valence complexes [Fe 2 (ì-OH)(AdaCO 2 ) 2 (R 3 tacn) 2 ]OTf 2 and [Fe 2 (ì-O)(AdaCO 2 ) 2 (R 3 tacn) 2 ]OTf (R = Bn or Me) were synthesized by the chemical oxidation of the parent diiron(II) complexes. The X-ray crystal structures of the MC 3 tacn complexes are reported. 1 H NMR studies showed these species to be stable in solution. |
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