{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/84350"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/84350","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Modeling the Active Sites of [nickel-Iron]- and [iron-Iron]-Hydrogenases","abstract":"While previous hydride-containing [FeFe]-hydrogenase models featured only bridging hydrides, we sought to prepare complexes of terminal hydrides that would be more relevant to mimicking this hydrogenase. Di-subferrous precursors, such as Fe2(S2C2H4)(CO)4 (PMe3)2, have been known for decades---well before the elucidation of the structure of the active site. Two-electron oxidation of Fe2(S2C2H4)(CO)4(PMe 3)2 in the presence of excess PMe3 in MeCN resulted in the formation of the diferrous [Fe2(S2C2H 4)(mu-CO)(NCMe)(CO)(PMe3)4](PF 6)2. This complex, when treated with hydride sources such as BH4- or AlH4- at low temperature, generated the first terminal hydride-containing [FeFe]-hydrogenase model complex, [HFe2(S2C2H4)(mu-CO)(CO)(PMe 3)4]PF6. This complex readily protonates with strong acids in MeCN to evolve H2 and regenerate the precursor MeCN-complex. The terminal hydride complex is thermally unstable, isomerizing to give an inert bridging hydride, even in the solid state.","abstract_html":"While previous hydride-containing [FeFe]-hydrogenase models featured only bridging hydrides, we sought to prepare complexes of terminal hydrides that would be more relevant to mimicking this hydrogenase. Di-subferrous precursors, such as Fe2(S2C2H4)(CO)4 (PMe3)2, have been known for decades---well before the elucidation of the structure of the active site. Two-electron oxidation of Fe2(S2C2H4)(CO)4(PMe 3)2 in the presence of excess PMe3 in MeCN resulted in the formation of the diferrous [Fe2(S2C2H 4)(mu-CO)(NCMe)(CO)(PMe3)4](PF 6)2. This complex, when treated with hydride sources such as BH4- or AlH4- at low temperature, generated the first terminal hydride-containing [FeFe]-hydrogenase model complex, [HFe2(S2C2H4)(mu-CO)(CO)(PMe 3)4]PF6. This complex readily protonates with strong acids in MeCN to evolve H2 and regenerate the precursor MeCN-complex. The terminal hydride complex is thermally unstable, isomerizing to give an inert bridging hydride, even in the solid state.","abstract_has_math":false,"creators":["Whaley, Curtis"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Thomas Rauchfuss"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2015,"date_issued":"2015-09-25T22:14:03Z","date_published":"2015-09-25T22:14:03Z","updated_at":"2026-07-22T22:26:23Z","subjects":["Chemistry, Inorganic"],"languages":["eng"],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(MiAaPQ)AAI3395535"],"render_values":[{"text":"(MiAaPQ)AAI3395535","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/84350","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Thomas Rauchfuss"]},{"key":"dc:creator","label":"Author","values":["Whaley, Curtis"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2015-09-25T22:14:03Z","10000-01-01","2009"]},{"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, Inorganic"]}]},{"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/2142/84350","(MiAaPQ)AAI3395535"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["While previous hydride-containing [FeFe]-hydrogenase models featured only bridging hydrides, we sought to prepare complexes of terminal hydrides that would be more relevant to mimicking this hydrogenase. Di-subferrous precursors, such as Fe2(S2C2H4)(CO)4 (PMe3)2, have been known for decades---well before the elucidation of the structure of the active site. Two-electron oxidation of Fe2(S2C2H4)(CO)4(PMe 3)2 in the presence of excess PMe3 in MeCN resulted in the formation of the diferrous [Fe2(S2C2H 4)(mu-CO)(NCMe)(CO)(PMe3)4](PF 6)2. This complex, when treated with hydride sources such as BH4- or AlH4- at low temperature, generated the first terminal hydride-containing [FeFe]-hydrogenase model complex, [HFe2(S2C2H4)(mu-CO)(CO)(PMe 3)4]PF6. This complex readily protonates with strong acids in MeCN to evolve H2 and regenerate the precursor MeCN-complex. The terminal hydride complex is thermally unstable, isomerizing to give an inert bridging hydride, even in the solid state.","Made available in DSpace on 2015-09-25T22:14:03Z (GMT). No. of bitstreams: 2 license.txt: 4848 bytes, checksum: 96035ab3f5e1c23cc7138a224ce498bd (MD5) 3395535.pdf: 1737126 bytes, checksum: 30406d1625c364b8829731341774d40f (MD5) Previous issue date: 2009","Embargo set by: Seth Robbins for item 85631 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","154 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 2009."]},{"key":"dc:title","label":"Title","values":["Modeling the Active Sites of [nickel-Iron]- and [iron-Iron]-Hydrogenases"]}]}],"canonical_facts":{"dc:contributor":["Thomas Rauchfuss"],"dc:creator":["Whaley, Curtis"],"dc:date":["2015-09-25T22:14:03Z","10000-01-01","2009"],"dc:description":["While previous hydride-containing [FeFe]-hydrogenase models featured only bridging hydrides, we sought to prepare complexes of terminal hydrides that would be more relevant to mimicking this hydrogenase. Di-subferrous precursors, such as Fe2(S2C2H4)(CO)4 (PMe3)2, have been known for decades---well before the elucidation of the structure of the active site. Two-electron oxidation of Fe2(S2C2H4)(CO)4(PMe 3)2 in the presence of excess PMe3 in MeCN resulted in the formation of the diferrous [Fe2(S2C2H 4)(mu-CO)(NCMe)(CO)(PMe3)4](PF 6)2. This complex, when treated with hydride sources such as BH4- or AlH4- at low temperature, generated the first terminal hydride-containing [FeFe]-hydrogenase model complex, [HFe2(S2C2H4)(mu-CO)(CO)(PMe 3)4]PF6. This complex readily protonates with strong acids in MeCN to evolve H2 and regenerate the precursor MeCN-complex. The terminal hydride complex is thermally unstable, isomerizing to give an inert bridging hydride, even in the solid state.","Made available in DSpace on 2015-09-25T22:14:03Z (GMT). No. of bitstreams: 2 license.txt: 4848 bytes, checksum: 96035ab3f5e1c23cc7138a224ce498bd (MD5) 3395535.pdf: 1737126 bytes, checksum: 30406d1625c364b8829731341774d40f (MD5) Previous issue date: 2009","Embargo set by: Seth Robbins for item 85631 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","154 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 2009."],"dc:identifier":["http://hdl.handle.net/2142/84350","(MiAaPQ)AAI3395535"],"dc:language":["eng"],"dc:subject":["Chemistry, Inorganic"],"dc:title":["Modeling the Active Sites of [nickel-Iron]- and [iron-Iron]-Hydrogenases"],"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":"2026-07-22T22:26:23Z"}