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


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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dc.contributor.author Myers, William
dc.date.accessioned 2009-01-30T16:24:24Z
dc.date.available 2009-01-30T16:24:24Z
dc.date.issued 2009-01-30T16:24:24Z
dc.date.submitted December 2008
dc.identifier.uri http://hdl.handle.net/1928/7652
dc.description.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). en_US
dc.language.iso en_US en_US
dc.subject Cobalt en_US
dc.subject ENDOR en_US
dc.subject high-spin cobalt en_US
dc.subject Bistrispyrazolylborate compounds. en_US
dc.subject.lcsh Cobalt compounds--Spectra.
dc.subject.lcsh Pyrazoles--Spectra.
dc.subject.lcsh Electron nuclear double resonance spectroscopy.
dc.subject.lcsh Metalloenzymes.
dc.title Paramagnetic resonance studies of bistrispyrazolylborate cobalt(II) and related derivatives en_US
dc.type Dissertation en_US
dc.description.degree Doctor of Chemistry en_US
dc.description.level Doctoral en_US
dc.description.department University of New Mexico. Dept. of Chemistry en_US
dc.description.advisor Tierney, David
dc.description.committee-member Kirk, Martin
dc.description.committee-member Guo, Hua
dc.description.committee-member Fukushima, Eiichi

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