University of Illinois Urbana-Champaign

Structural and Spectroscopic Models of the [iron-Iron]-Hydrogenase Enzyme

Justice, Aaron

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Description

Title
Structural and Spectroscopic Models of the [iron-Iron]-Hydrogenase Enzyme
Author(s)
Justice, Aaron
Issue Date
2008
Doctoral Committee Chair(s)
Thomas Rauchfuss
Department of Study
Chemistry
Discipline
Chemistry
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(s)
Chemistry, Physical
Language
eng
Abstract
The unsaturated character of [1(CO)3(PMe 3)]+ is indicated by its reactivity with CO, which occurs in seconds. The product; [Fe2(S2C2H 4)(mu-CO)(CO)3(PMe3)(dppv)]+ [1(CO)4(PMe3)]+ is highly unstable and could only be observed under a CO atmosphere. The EPR spectrum for [1(CO)4(PMe3)]+ featured a doublet of triplets, coupled to three phosphorus nuclei with two distinct phosphorus hyperfine couplings (A(31P) = 283, 32 and 34 MHz). Based upon the changes in the EPR, upon binding CO the unpaired spin becomes delocalized over both iron centers resulting in two Fe(1.5) metal centers.
Graduation Semester
2008
Type of Resource
text
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http://hdl.handle.net/2142/84298

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