{"@context":"http://iiif.io/api/presentation/2/context.json","@id":"https://repo.library.stonybrook.edu/cantaloupe/iiif/2/manifest.json","@type":"sc:Manifest","label":"Metal Complexes for Structural Modeling of Active Sites of Metalloenzymes Relevant to Gas Catalysis","metadata":[{"label":"dc.description.sponsorship","value":"This work is sponsored by the Stony Brook University Graduate School in compliance with the requirements for completion of degree."},{"label":"dc.format","value":"Monograph"},{"label":"dc.format.medium","value":"Electronic Resource"},{"label":"dc.identifier.uri","value":"http://hdl.handle.net/11401/77089"},{"label":"dc.language.iso","value":"en_US"},{"label":"dc.publisher","value":"The Graduate School, Stony Brook University: Stony Brook, NY."},{"label":"dcterms.abstract","value":"Sulfur rich metal coordinated active sites is a prominent feature of many metalloenzymes (hydrogenase, nitrogenase, carbon monoxide dehydrogenase) involved in catalytically producing and/or absorbing helpful and/or toxic gases. As the mechanism of gas production and/or absorption heavily depends on the structural intricacies, biomimetic modelling of the active sites is of paramount importance to understand the structure-function relationship. It has been established that the small molecule models with steric bulk of the thiols at the ortho- position of derivatized benzenethiols can provide the stability. Millar and Koch were pioneers in introducing a series of ortho-steric benzene thiols and achieving stabilization of high oxidation state first row transition metal complexes. Fe<super>3+</super> & Co<super>3+</super> complexes and Fe<sub>4</sub>S<sub>4</sub> tertamer with 2,4,6-triisopropyl-benzenethiol are the highlights. Following the idea of increasing the steric bulk, this thesis will present a new compound - 2,4,6-tricyclohexylbenzenethiol, and attempted synthesis and characterization of monomeric and tetrameric metal complexes with it.  Dithiols such as ethanedithiol (edt) and 1,2-benzenedithiol (bdt) have been extensively used for synthesizing models due to their simplicity in structure. While edt lacks the required steric bulk, bdt is a non-innocent ligand influencing electrochemical properties of the complexes. To combat these difficulties, a new class of dithiol was introduced by Michelle Millar and Stephen Koch - norbornanedithiol - a conformationally fixed alkane dithiol. Metal complexes with Fe<super>2+</super>, Co<super>2+</super>, Ni<super>2+</super> & Pt<super>2+</super> will be discussed. Hydrogen bonding of the solvent molecules to the thiolates and the implications of such observation will be presented. Fe-Ni hydrogenases are responsible for converting H<sub>2</sub> gas to H<super>+</super>. This class of enzyme contains a bimetallic active site. In our effort to mimic the structure, we have crystallographically characterized Fe-Ni bimetallic compounds with bridged thiolates and intermetallic distance of ~3\u00c3\u2026 as found in the wild type from Desulfovibrio gigas. An extensive IR study of the reaction and the compounds will be presented."},{"label":"dcterms.available","value":"2017-09-20T16:51:56Z"},{"label":"dcterms.contributor","value":"Mayr, Andreas"},{"label":"dcterms.creator","value":"Bhattacharya, Soumya"},{"label":"dcterms.dateAccepted","value":"2017-09-20T16:51:56Z"},{"label":"dcterms.dateSubmitted","value":"2017-09-20T16:51:56Z"},{"label":"dcterms.description","value":"Department of Chemistry."},{"label":"dcterms.extent","value":"152 pg."},{"label":"dcterms.format","value":"Monograph"},{"label":"dcterms.identifier","value":"http://hdl.handle.net/11401/77089"},{"label":"dcterms.issued","value":"2014-12-01"},{"label":"dcterms.language","value":"en_US"},{"label":"dcterms.provenance","value":"Made available in DSpace on 2017-09-20T16:51:56Z (GMT). No. of bitstreams: 1\nBhattacharya_grad.sunysb_0771E_11966.pdf: 4164843 bytes, checksum: e016776a42703f0d72a4c6f063807808 (MD5)\n  Previous issue date:    1"},{"label":"dcterms.publisher","value":"The Graduate School, Stony Brook University: Stony Brook, NY."},{"label":"dcterms.subject","value":"biomimetic modelling, metalloenzyme"},{"label":"dcterms.title","value":"Metal Complexes for Structural Modeling of Active Sites of Metalloenzymes Relevant to Gas Catalysis"},{"label":"dcterms.type","value":"Dissertation"},{"label":"dc.type","value":"Dissertation"}],"description":"This manifest was generated dynamically","viewingDirection":"left-to-right","sequences":[{"@type":"sc:Sequence","canvases":[{"@id":"https://repo.library.stonybrook.edu/cantaloupe/iiif/2/canvas/page-1.json","@type":"sc:Canvas","label":"Page 1","height":1650,"width":1275,"images":[{"@type":"oa:Annotation","motivation":"sc:painting","resource":{"@id":"https://repo.library.stonybrook.edu/cantaloupe/iiif/2/10%2F11%2F29%2F10112933843965508084646036219436823270/full/full/0/default.jpg","@type":"dctypes:Image","format":"image/jpeg","height":1650,"width":1275,"service":{"@context":"http://iiif.io/api/image/2/context.json","@id":"https://repo.library.stonybrook.edu/cantaloupe/iiif/2/10%2F11%2F29%2F10112933843965508084646036219436823270","profile":"http://iiif.io/api/image/2/level2.json"}},"on":"https://repo.library.stonybrook.edu/cantaloupe/iiif/2/canvas/page-1.json"}]}]}]}