University of Illinois Urbana-Champaign

Biologically-Inspired Bimetallic Complexes for the Activation of Small Molecules

Linck, Rachel Clare

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Description

Title
Biologically-Inspired Bimetallic Complexes for the Activation of Small Molecules
Author(s)
Linck, Rachel Clare
Issue Date
2004
Doctoral Committee Chair(s)
Rauchfuss, Thomas B.
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, Biochemistry
Language
eng
Abstract
The activation of dihydrogen has only been observed indirectly through the photolytically-induced H/D exchange of [Fe2(mu-H)(SR) 2(CO)4(PR3)2]+ Fe-only hydrogenase models with D2. The diphosphine diruthenium complex Ru2(S2C3H6)(CO)4(PCy 3)2 oxidatively adds dihydrogen to produce the dihydride Ru2(S2C3H6)(mu-H)(H)(CO) 3(PCy3)2, the first example of the homolytic activation of dihydrogen by a synthetic Fe-only hydrogenase model. The protonation of the terminal hydride ligand of Ru2(S2C3H 6)(mu-H)(H)(CO)3(PCy3)2 has the potential to produce the first synthetic model of the Fe-only hydrogenase enzyme with a bound dihydrogen ligand. While these models are based on diruthenium systems rather than diiron systems, comparison of the iron-based enzyme to synthetic ruthenium mimics may lead to innovations in the preparation of biologically-inspired catalysts.
Graduation Semester
2004
Type of Resource
text
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http://hdl.handle.net/2142/84156

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