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

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.

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Illinois at Urbana-Champaign

Year dc:date

2015

Author dc:creator

• Justice, Aaron

Contributors dc:contributor

• Thomas Rauchfuss

• Chemistry, Physical

Language dc:language

eng

Identifier

(MiAaPQ)AAI3314961

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/84298