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.contributor.advisor | Rose, Michael J., Ph. D. | en |
| dc.contributor.committeeMember | Holliday, Bradley J | en |
| dc.creator | Thomas Muthiah, Keren Arunothayam | en |
| dc.date.accessioned | 2015-10-16T18:13:05Z | en |
| dc.date.available | 2015-10-16T18:13:05Z | en |
| dc.date.issued | 2014-08 | en |
| dc.date.submitted | August 2014 | en |
| dc.date.updated | 2015-10-16T18:13:05Z | en |
| dc.description | text | en |
| 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. | en |
| dc.description.department | Chemistry | en |
| dc.format.mimetype | application/pdf | en |
| dc.identifier | doi:10.15781/T2H60S | en |
| dc.identifier.uri | http://hdl.handle.net/2152/31751 | en |
| dc.language.iso | en | en |
| dc.subject | Hydrogenase | en |
| dc.subject | Fe complexes | en |
| 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 | en |
| dc.type | Thesis | en |
| thesis.degree.department | Chemistry | en |
| thesis.degree.discipline | Chemistry | en |
| thesis.degree.grantor | The University of Texas at Austin | en |
| thesis.degree.level | Masters | en |
| thesis.degree.name | Master of Arts | en |