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Paramagnetic resonance studies of bistrispyrazolylborate cobalt(II) and related derivatives

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Please use this identifier to cite or link to this item: http://hdl.handle.net/1928/7652

Paramagnetic resonance studies of bistrispyrazolylborate cobalt(II) and related derivatives

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Title: Paramagnetic resonance studies of bistrispyrazolylborate cobalt(II) and related derivatives
Author: Myers, William
Advisor(s): Tierney, David
Committee Member(s): Kirk, Martin
Guo, Hua
Fukushima, Eiichi
Department: University of New Mexico. Dept. of Chemistry
Subject: Cobalt
ENDOR
high-spin cobalt
Bistrispyrazolylborate compounds.
LC Subject(s): Cobalt compounds--Spectra.
Pyrazoles--Spectra.
Electron nuclear double resonance spectroscopy.
Metalloenzymes.
Degree Level: Doctoral
Abstract: Herein, a systematic frozen solution electron-nuclear double resonance (ENDOR) study of high-spin Co(II) complexes is reported to demonstrate the efficacy of methyl substitutions as a means of separating dipolar and contact coupling, and further, to increase the utility of high-spin Co(II) as a spectroscopic probe for the ubiquitous, but spectroscopically-silent Zn(II) metalloenzymes. High-spin (hs) Co(II) has been subject of paramagnetic resonance studies for over 50 years and has been used as a spectroscopic probe for Zn metalloenzymes for over 35 years. However, as will be seen, the inherent complexity of the electronic properties of the cobaltous ion remains to be exploited to offer a wealth of information on Zn(II) enzymatic environments. Specifically, ENDOR measurements on bistrispyrazolylborate cobalt(II) confirm the utility of the novel method of methyl substitution to differentiate dipolar and Fermi contact couplings. An extensive set of electron paramagnetic resonance (EPR) simulations were performed. Software was developed to implement an ENDOR control interface. Finally, proton relaxation measurements were made in the range of 12-42 MHz, which were accounted for with the large g-value anisotropy of the Co(II) compounds. Taken as a whole, these studies point to the rich complexity of the electronic structure of high-spin cobalt(II) and, when sufficiently well-characterized, the great utility it has as a surrogate of biological Zn(II).
Graduation Date: December 2008
URI: http://hdl.handle.net/1928/7652


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