{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/84354"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/84354","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Hydrogen Production From Model Complexes of the [iron-Iron]- and [nickel-Iron]-Hydrogenase Active Sites","abstract":"Unlike the [FeFe]-hydrogenases, model complexes for the [NiFe]-hydrogenases were unknown prior to the crystal structure in 1996. However, most synthetic efforts focused on structural models for the active site, and neglected the catalytically imperative hydride ligand. Thus, we sought a nickel-iron hydride complex to explore the relevant reactivity of the first (mu-H)Ni(mu-SR) 2Fe complex. We found that the previously reported (dppe)Ni(mu-pdt)Fe(CO) 3, a Ni(I)Fe(I) complex, reacted with acid to provide [(dppe)Ni(mu-H)(mu-pdt)Fe(CO) 3]+, the first nickel-iron hydride. After protonation, the hydride complex is amenable to substitution chemistry at the Fe(CO) 3 subunit. Further derivatives altering the Ni(diphosphine)(SR) 2 subunit have been achieved through an alternative synthetic procedure to the Ni(I)Fe(I) complex. All nickel-iron hydrides investigated are active catalysts for the reduction of protons. As the catalytic mechanism of [NiFe]-hydrogenase is widely speculative, the reactivity of this new class of nickel-iron hydrides offers powerful insights into Nature's catalytic mechanism. (Abstract shortened by UMI.).","abstract_html":"Unlike the [FeFe]-hydrogenases, model complexes for the [NiFe]-hydrogenases were unknown prior to the crystal structure in 1996. However, most synthetic efforts focused on structural models for the active site, and neglected the catalytically imperative hydride ligand. Thus, we sought a nickel-iron hydride complex to explore the relevant reactivity of the first (mu-H)Ni(mu-SR) 2Fe complex. We found that the previously reported (dppe)Ni(mu-pdt)Fe(CO) 3, a Ni(I)Fe(I) complex, reacted with acid to provide [(dppe)Ni(mu-H)(mu-pdt)Fe(CO) 3]+, the first nickel-iron hydride. After protonation, the hydride complex is amenable to substitution chemistry at the Fe(CO) 3 subunit. Further derivatives altering the Ni(diphosphine)(SR) 2 subunit have been achieved through an alternative synthetic procedure to the Ni(I)Fe(I) complex. All nickel-iron hydrides investigated are active catalysts for the reduction of protons. As the catalytic mechanism of [NiFe]-hydrogenase is widely speculative, the reactivity of this new class of nickel-iron hydrides offers powerful insights into Nature's catalytic mechanism. (Abstract shortened by UMI.).","abstract_has_math":false,"creators":["Barton, Bryan E."],"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":"2015-09-25T22:14:05Z","date_published":"2015-09-25T22:14:05Z","updated_at":"2026-07-22T22:26:23Z","subjects":["Chemistry, Inorganic"],"languages":["eng"],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(MiAaPQ)AAI3455686"],"render_values":[{"text":"(MiAaPQ)AAI3455686","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/84354","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":["Barton, Bryan E."]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2015-09-25T22:14:05Z","10000-01-01","2010"]},{"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/2142/84354","(MiAaPQ)AAI3455686"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Unlike the [FeFe]-hydrogenases, model complexes for the [NiFe]-hydrogenases were unknown prior to the crystal structure in 1996. However, most synthetic efforts focused on structural models for the active site, and neglected the catalytically imperative hydride ligand. Thus, we sought a nickel-iron hydride complex to explore the relevant reactivity of the first (mu-H)Ni(mu-SR) 2Fe complex. We found that the previously reported (dppe)Ni(mu-pdt)Fe(CO) 3, a Ni(I)Fe(I) complex, reacted with acid to provide [(dppe)Ni(mu-H)(mu-pdt)Fe(CO) 3]+, the first nickel-iron hydride. After protonation, the hydride complex is amenable to substitution chemistry at the Fe(CO) 3 subunit. Further derivatives altering the Ni(diphosphine)(SR) 2 subunit have been achieved through an alternative synthetic procedure to the Ni(I)Fe(I) complex. All nickel-iron hydrides investigated are active catalysts for the reduction of protons. As the catalytic mechanism of [NiFe]-hydrogenase is widely speculative, the reactivity of this new class of nickel-iron hydrides offers powerful insights into Nature's catalytic mechanism. (Abstract shortened by UMI.).","Made available in DSpace on 2015-09-25T22:14:05Z (GMT). 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However, most synthetic efforts focused on structural models for the active site, and neglected the catalytically imperative hydride ligand. Thus, we sought a nickel-iron hydride complex to explore the relevant reactivity of the first (mu-H)Ni(mu-SR) 2Fe complex. We found that the previously reported (dppe)Ni(mu-pdt)Fe(CO) 3, a Ni(I)Fe(I) complex, reacted with acid to provide [(dppe)Ni(mu-H)(mu-pdt)Fe(CO) 3]+, the first nickel-iron hydride. After protonation, the hydride complex is amenable to substitution chemistry at the Fe(CO) 3 subunit. Further derivatives altering the Ni(diphosphine)(SR) 2 subunit have been achieved through an alternative synthetic procedure to the Ni(I)Fe(I) complex. All nickel-iron hydrides investigated are active catalysts for the reduction of protons. As the catalytic mechanism of [NiFe]-hydrogenase is widely speculative, the reactivity of this new class of nickel-iron hydrides offers powerful insights into Nature's catalytic mechanism. (Abstract shortened by UMI.).","Made available in DSpace on 2015-09-25T22:14:05Z (GMT). No. of bitstreams: 2 license.txt: 4848 bytes, checksum: 96035ab3f5e1c23cc7138a224ce498bd (MD5) 3455686.pdf: 6193860 bytes, checksum: c35dd0348ac7c1f93f5baf8a7514369b (MD5) Previous issue date: 2010","Embargo set by: Seth Robbins for item 85635 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","273 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 2010."],"dc:identifier":["http://hdl.handle.net/2142/84354","(MiAaPQ)AAI3455686"],"dc:language":["eng"],"dc:subject":["Chemistry, Inorganic"],"dc:title":["Hydrogen Production From Model Complexes of the [iron-Iron]- and [nickel-Iron]-Hydrogenase Active Sites"],"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"}