{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/84217"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/84217","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Diferrous Structural and Functional Models of the Iron-Only Hydrogenases","abstract":"Low temperature IR spectroscopic studies show that the protonation of (Et4N)2[Fe2(S2C3H 6)(CN)2(CO)4] with HOTs gave Et4N[Fe 2(S2C3H6)(CN)(CNH)(CO)4]. Et4N[Fe2(S2C3H6)(CN)(CNH)(CO) 4] undergoes an approximate first-order decay to the hydride, Et 4N[HFe2(S2C3H6)(CN) 2(CO)4]. Addition of a second equiv of H+ to Et4N[HFe2(S2C3H6)(CN) 2(CO)4] resulted in protonation at the CN-ligand to give [HFe2(S2C3H6)(CN)(CNH)(CO) 4. Decarbonylation of Et4N[HFe2(S2C 3H6)(CN)2(CO)4] in the presence of PPh3 resulted in Et4N[HFe2(S2C 3H6)(CN)2(CO)3(PPh3)] followed by Et4N[HFe2(S2C3H6)(CN) 2(CO)2(PPh3)2], which exist as multiple isomers. Photolysis of McCN solutions of Et4N[HFe2(S 2C3H6)(CN)2(CO)4] in the absence of PPh3 gave the solvolysis product, Et4N[HFe 2(S2C3H6)(CN)2(MeCN)(CO) 3]. Et4N[HFe2(S2C3H 6)(CN)2(MeCN)(CO)3] reacted with PMe3 and CN to produce (Et4N)[HFe2(S2C3H 6)(CN)2(PMe3)(CO)3] and (Et4N) 2[HFe2(S2C3H6)(CN) 3(CO)3].","abstract_html":"Low temperature IR spectroscopic studies show that the protonation of (Et4N)2[Fe2(S2C3H 6)(CN)2(CO)4] with HOTs gave Et4N[Fe 2(S2C3H6)(CN)(CNH)(CO)4]. Et4N[Fe2(S2C3H6)(CN)(CNH)(CO) 4] undergoes an approximate first-order decay to the hydride, Et 4N[HFe2(S2C3H6)(CN) 2(CO)4]. Addition of a second equiv of H+ to Et4N[HFe2(S2C3H6)(CN) 2(CO)4] resulted in protonation at the CN-ligand to give [HFe2(S2C3H6)(CN)(CNH)(CO) 4. Decarbonylation of Et4N[HFe2(S2C 3H6)(CN)2(CO)4] in the presence of PPh3 resulted in Et4N[HFe2(S2C 3H6)(CN)2(CO)3(PPh3)] followed by Et4N[HFe2(S2C3H6)(CN) 2(CO)2(PPh3)2], which exist as multiple isomers. Photolysis of McCN solutions of Et4N[HFe2(S 2C3H6)(CN)2(CO)4] in the absence of PPh3 gave the solvolysis product, Et4N[HFe 2(S2C3H6)(CN)2(MeCN)(CO) 3]. Et4N[HFe2(S2C3H 6)(CN)2(MeCN)(CO)3] reacted with PMe3 and CN to produce (Et4N)[HFe2(S2C3H 6)(CN)2(PMe3)(CO)3] and (Et4N) 2[HFe2(S2C3H6)(CN) 3(CO)3].","abstract_has_math":false,"creators":["Boyke, Christine A."],"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":"2015-09-25T22:13:31Z","date_published":"2015-09-25T22:13:31Z","updated_at":"2026-07-22T22:26:22Z","subjects":["Chemistry, Inorganic"],"languages":["eng"],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(MiAaPQ)AAI3223548"],"render_values":[{"text":"(MiAaPQ)AAI3223548","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/84217","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":["Boyke, Christine A."]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2015-09-25T22:13:31Z","10000-01-01","2006"]},{"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/2142/84217","(MiAaPQ)AAI3223548"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Low temperature IR spectroscopic studies show that the protonation of (Et4N)2[Fe2(S2C3H 6)(CN)2(CO)4] with HOTs gave Et4N[Fe 2(S2C3H6)(CN)(CNH)(CO)4]. Et4N[Fe2(S2C3H6)(CN)(CNH)(CO) 4] undergoes an approximate first-order decay to the hydride, Et 4N[HFe2(S2C3H6)(CN) 2(CO)4]. Addition of a second equiv of H+ to Et4N[HFe2(S2C3H6)(CN) 2(CO)4] resulted in protonation at the CN-ligand to give [HFe2(S2C3H6)(CN)(CNH)(CO) 4. Decarbonylation of Et4N[HFe2(S2C 3H6)(CN)2(CO)4] in the presence of PPh3 resulted in Et4N[HFe2(S2C 3H6)(CN)2(CO)3(PPh3)] followed by Et4N[HFe2(S2C3H6)(CN) 2(CO)2(PPh3)2], which exist as multiple isomers. Photolysis of McCN solutions of Et4N[HFe2(S 2C3H6)(CN)2(CO)4] in the absence of PPh3 gave the solvolysis product, Et4N[HFe 2(S2C3H6)(CN)2(MeCN)(CO) 3]. Et4N[HFe2(S2C3H 6)(CN)2(MeCN)(CO)3] reacted with PMe3 and CN to produce (Et4N)[HFe2(S2C3H 6)(CN)2(PMe3)(CO)3] and (Et4N) 2[HFe2(S2C3H6)(CN) 3(CO)3].","Made available in DSpace on 2015-09-25T22:13:31Z (GMT). No. of bitstreams: 2 license.txt: 4848 bytes, checksum: 96035ab3f5e1c23cc7138a224ce498bd (MD5) 3223548.pdf: 3828286 bytes, checksum: 0b17194e2bd4bb0c08a130876eba167e (MD5) Previous issue date: 2006","Embargo set by: Seth Robbins for item 85498 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","178 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 2006."]},{"key":"dc:title","label":"Title","values":["Diferrous Structural and Functional Models of the Iron-Only Hydrogenases"]}]}],"canonical_facts":{"dc:contributor":["Rauchfuss, Thomas B."],"dc:creator":["Boyke, Christine A."],"dc:date":["2015-09-25T22:13:31Z","10000-01-01","2006"],"dc:description":["Low temperature IR spectroscopic studies show that the protonation of (Et4N)2[Fe2(S2C3H 6)(CN)2(CO)4] with HOTs gave Et4N[Fe 2(S2C3H6)(CN)(CNH)(CO)4]. Et4N[Fe2(S2C3H6)(CN)(CNH)(CO) 4] undergoes an approximate first-order decay to the hydride, Et 4N[HFe2(S2C3H6)(CN) 2(CO)4]. Addition of a second equiv of H+ to Et4N[HFe2(S2C3H6)(CN) 2(CO)4] resulted in protonation at the CN-ligand to give [HFe2(S2C3H6)(CN)(CNH)(CO) 4. Decarbonylation of Et4N[HFe2(S2C 3H6)(CN)2(CO)4] in the presence of PPh3 resulted in Et4N[HFe2(S2C 3H6)(CN)2(CO)3(PPh3)] followed by Et4N[HFe2(S2C3H6)(CN) 2(CO)2(PPh3)2], which exist as multiple isomers. Photolysis of McCN solutions of Et4N[HFe2(S 2C3H6)(CN)2(CO)4] in the absence of PPh3 gave the solvolysis product, Et4N[HFe 2(S2C3H6)(CN)2(MeCN)(CO) 3]. Et4N[HFe2(S2C3H 6)(CN)2(MeCN)(CO)3] reacted with PMe3 and CN to produce (Et4N)[HFe2(S2C3H 6)(CN)2(PMe3)(CO)3] and (Et4N) 2[HFe2(S2C3H6)(CN) 3(CO)3].","Made available in DSpace on 2015-09-25T22:13:31Z (GMT). No. of bitstreams: 2 license.txt: 4848 bytes, checksum: 96035ab3f5e1c23cc7138a224ce498bd (MD5) 3223548.pdf: 3828286 bytes, checksum: 0b17194e2bd4bb0c08a130876eba167e (MD5) Previous issue date: 2006","Embargo set by: Seth Robbins for item 85498 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","178 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 2006."],"dc:identifier":["http://hdl.handle.net/2142/84217","(MiAaPQ)AAI3223548"],"dc:language":["eng"],"dc:subject":["Chemistry, Inorganic"],"dc:title":["Diferrous Structural and Functional Models of the Iron-Only 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":"2026-07-22T22:26:22Z"}