{"id":{"repo_id":"texas","oai_identifier":"oai:repositories.lib.utexas.edu:2152/31751"},"canonical_url":"https://search.dev.ndltd.org/etd/texas/oai:repositories.lib.utexas.edu:2152/31751","repository":{"repo_id":"texas","name":"University of Texas","base_url":"https://repositories.lib.utexas.edu/server/oai/request"},"display":{"title":"Synthesis and stabilities of mononuclear iron (II) dicarbonyls derived from neutral NNS ligands : structural models of the apo-active site of mono-iron (Hmd) hydrogenase","abstract":"Herein is described the syntheses and characterization of iron dicarbonyl complexes derived from tridentate ortho-substituted Schiff base pyridine/thioether ligands ([subscript R]NNS) and (Fe(CO)₄(Br)₂). Two general synthetic routes are reported for the isolation of such iron carbonyls. First, metalation of [subscript R]NNS ligands within Et₂O at room temperature affords the complex species of type (([subscript R]NNS)Fe(CO)₂Br)(Fe(CO)₃(Br)₃). Alternatively, metalations of [subscript R]NNS (R = CH₃, OCH₃) at low temperature (-78 °C) in CH₂Cl₂/MeCN mixtures with (Fe(CO)₄(Br)₂) afford complexes of formula ([subscript R]NNS)Fe(CO)₂Br)Br. Reactions under similar conditions with more sterically demanding ligands (R = quinoline (Q), chlorophenyl (ClPh)) afford a complex salt of the form (([subscript R]NNS)Fe(CO)₂Br)(Fe(CO)₃(Br)₃). Complexes have been characterized using X-ray crystallography, IR spectroscopy and low temperature ¹H NMR spectroscopy. Photostability of the complexes has been studied using UV-vis and solution IR spectroscopies. Relevance to the apo-active site of mono-iron hydrogenase is discussed.","abstract_html":"Herein is described the syntheses and characterization of iron dicarbonyl complexes derived from tridentate ortho-substituted Schiff base pyridine/thioether ligands ([subscript R]NNS) and (Fe(CO)₄(Br)₂). Two general synthetic routes are reported for the isolation of such iron carbonyls. First, metalation of [subscript R]NNS ligands within Et₂O at room temperature affords the complex species of type (([subscript R]NNS)Fe(CO)₂Br)(Fe(CO)₃(Br)₃). Alternatively, metalations of [subscript R]NNS (R = CH₃, OCH₃) at low temperature (-78 °C) in CH₂Cl₂/MeCN mixtures with (Fe(CO)₄(Br)₂) afford complexes of formula ([subscript R]NNS)Fe(CO)₂Br)Br. Reactions under similar conditions with more sterically demanding ligands (R = quinoline (Q), chlorophenyl (ClPh)) afford a complex salt of the form (([subscript R]NNS)Fe(CO)₂Br)(Fe(CO)₃(Br)₃). Complexes have been characterized using X-ray crystallography, IR spectroscopy and low temperature ¹H NMR spectroscopy. Photostability of the complexes has been studied using UV-vis and solution IR spectroscopies. Relevance to the apo-active site of mono-iron hydrogenase is discussed.","abstract_has_math":false,"creators":["Thomas Muthiah, Keren Arunothayam"],"institution":"The University of Texas at Austin","degree_name":"Master of Arts","degree_level":"Masters","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":[],"advisors":["Rose, Michael J., Ph. D."],"committee_chairs":[],"committee_members":["Holliday, Bradley J"],"year":2014,"date_issued":"2014-08","date_published":"2014-08","updated_at":"2026-07-24T05:00:56Z","subjects":["Hydrogenase","Fe complexes"],"languages":["en"],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["doi:10.15781/T2H60S"],"render_values":[{"text":"doi:10.15781/T2H60S","href":"https://doi.org/10.15781/T2H60S","code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2152/31751","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Rose, Michael J., Ph. 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Two general synthetic routes are reported for the isolation of such iron carbonyls. First, metalation of [subscript R]NNS ligands within Et₂O at room temperature affords the complex species of type (([subscript R]NNS)Fe(CO)₂Br)(Fe(CO)₃(Br)₃). Alternatively, metalations of [subscript R]NNS (R = CH₃, OCH₃) at low temperature (-78 °C) in CH₂Cl₂/MeCN mixtures with (Fe(CO)₄(Br)₂) afford complexes of formula ([subscript R]NNS)Fe(CO)₂Br)Br. Reactions under similar conditions with more sterically demanding ligands (R = quinoline (Q), chlorophenyl (ClPh)) afford a complex salt of the form (([subscript R]NNS)Fe(CO)₂Br)(Fe(CO)₃(Br)₃). Complexes have been characterized using X-ray crystallography, IR spectroscopy and low temperature ¹H NMR spectroscopy. Photostability of the complexes has been studied using UV-vis and solution IR spectroscopies. Relevance to the apo-active site of mono-iron hydrogenase is discussed."]},{"key":"dc:format.mimetype","label":"Dc Format Mimetype","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["Synthesis and stabilities of mononuclear iron (II) dicarbonyls derived from neutral NNS ligands : structural models of the apo-active site of mono-iron (Hmd) hydrogenase"]}]}],"canonical_facts":{"dc:contributor.advisor":["Rose, Michael J., Ph. D."],"dc:contributor.committeemember":["Holliday, Bradley J"],"dc:creator":["Thomas Muthiah, Keren Arunothayam"],"dc:date.accessioned":["2015-10-16T18:13:05Z"],"dc:date.available":["2015-10-16T18:13:05Z"],"dc:date.issued":["2014-08"],"dc:description":["text"],"dc:description.abstract":["Herein is described the syntheses and characterization of iron dicarbonyl complexes derived from tridentate ortho-substituted Schiff base pyridine/thioether ligands ([subscript R]NNS) and (Fe(CO)₄(Br)₂). Two general synthetic routes are reported for the isolation of such iron carbonyls. First, metalation of [subscript R]NNS ligands within Et₂O at room temperature affords the complex species of type (([subscript R]NNS)Fe(CO)₂Br)(Fe(CO)₃(Br)₃). Alternatively, metalations of [subscript R]NNS (R = CH₃, OCH₃) at low temperature (-78 °C) in CH₂Cl₂/MeCN mixtures with (Fe(CO)₄(Br)₂) afford complexes of formula ([subscript R]NNS)Fe(CO)₂Br)Br. Reactions under similar conditions with more sterically demanding ligands (R = quinoline (Q), chlorophenyl (ClPh)) afford a complex salt of the form (([subscript R]NNS)Fe(CO)₂Br)(Fe(CO)₃(Br)₃). Complexes have been characterized using X-ray crystallography, IR spectroscopy and low temperature ¹H NMR spectroscopy. Photostability of the complexes has been studied using UV-vis and solution IR spectroscopies. Relevance to the apo-active site of mono-iron hydrogenase is discussed."],"dc:format.mimetype":["application/pdf"],"dc:identifier":["doi:10.15781/T2H60S"],"dc:identifier.uri":["http://hdl.handle.net/2152/31751"],"dc:language.iso":["en"],"dc:subject":["Hydrogenase","Fe complexes"],"dc:title":["Synthesis and stabilities of mononuclear iron (II) dicarbonyls derived from neutral NNS ligands : structural models of the apo-active site of mono-iron (Hmd) hydrogenase"],"dc:type":["Thesis"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Masters"],"thesis:degree_name":["Master of Arts"],"thesis:institution_name":["The University of Texas at Austin"]},"updated_at":"2026-07-24T05:00:56Z"}