Biologically-Inspired Bimetallic Complexes for the Activation of Small Molecules

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.

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

• Linck, Rachel Clare

Contributors dc:contributor

• Rauchfuss, Thomas B.

• Chemistry, Biochemistry

Language dc:language

eng

Identifier

(MiAaPQ)AAI3153365

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/84156