{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/84156"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/84156","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Biologically-Inspired Bimetallic Complexes for the Activation of Small Molecules","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.","abstract_html":"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.","abstract_has_math":false,"creators":["Linck, Rachel Clare"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Rauchfuss, Thomas B."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2015,"date_issued":"2015-09-25T22:13:14Z","date_published":"2015-09-25T22:13:14Z","updated_at":"2026-07-22T22:26:22Z","subjects":["Chemistry, Biochemistry"],"languages":["eng"],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(MiAaPQ)AAI3153365"],"render_values":[{"text":"(MiAaPQ)AAI3153365","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/84156","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Rauchfuss, Thomas B."]},{"key":"dc:creator","label":"Author","values":["Linck, Rachel Clare"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2015-09-25T22:13:14Z","10000-01-01","2004"]},{"key":"dc:type","label":"Dc Type","values":["text"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Dissertation"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Ph.D."]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["University of Illinois at Urbana-Champaign"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Chemistry, Biochemistry"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["eng"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/84156","(MiAaPQ)AAI3153365"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["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.","Made available in DSpace on 2015-09-25T22:13:14Z (GMT). No. of bitstreams: 2 license.txt: 4848 bytes, checksum: 96035ab3f5e1c23cc7138a224ce498bd (MD5) 3153365.pdf: 14074644 bytes, checksum: f1c31ba6084de80f3bed6651c10f253c (MD5) Previous issue date: 2004","Embargo set by: Seth Robbins for item 85437 Lift date: Forever Reason: Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","U of I Only","219 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 2004."]},{"key":"dc:title","label":"Title","values":["Biologically-Inspired Bimetallic Complexes for the Activation of Small Molecules"]}]}],"canonical_facts":{"dc:contributor":["Rauchfuss, Thomas B."],"dc:creator":["Linck, Rachel Clare"],"dc:date":["2015-09-25T22:13:14Z","10000-01-01","2004"],"dc:description":["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.","Made available in DSpace on 2015-09-25T22:13:14Z (GMT). No. of bitstreams: 2 license.txt: 4848 bytes, checksum: 96035ab3f5e1c23cc7138a224ce498bd (MD5) 3153365.pdf: 14074644 bytes, checksum: f1c31ba6084de80f3bed6651c10f253c (MD5) Previous issue date: 2004","Embargo set by: Seth Robbins for item 85437 Lift date: Forever Reason: Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","U of I Only","219 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 2004."],"dc:identifier":["http://hdl.handle.net/2142/84156","(MiAaPQ)AAI3153365"],"dc:language":["eng"],"dc:subject":["Chemistry, Biochemistry"],"dc:title":["Biologically-Inspired Bimetallic Complexes for the Activation of Small Molecules"],"dc:type":["text"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Dissertation"],"thesis:degree_name":["Ph.D."],"thesis:institution_name":["University of Illinois at Urbana-Champaign"]},"updated_at":"2026-07-22T22:26:22Z"}