{"id":{"repo_id":"lsu-thes","oai_identifier":"oai:repository.lsu.edu:gradschool_dissertations-2435"},"canonical_url":"https://search.dev.ndltd.org/etd/lsu-thes/oai:repository.lsu.edu:gradschool_dissertations-2435","repository":{"repo_id":"lsu-thes","name":"Lousiana State University","base_url":"https://repository.lsu.edu/do/oai/"},"display":{"title":"Exploring the binding of amine and sulfonamide ligands in Rhenium(I) Tricarbonyl and Platinum(II) complexes","abstract":"Platinum is the metal present in various classes of inorganic medicinal agents directed at important diseases such as cancer or viral infections. Several new Pt(II) complexes of polyamine ligands bearing a dansyl moiety linked by a sulfonamide group were prepared; in some cases the sulfonamide nitrogen formed a bond to Pt. The sulfonamido group donates strongly to Pt and places the dansyl group close to a vacant coordination position, allowing it to stack with bound guanine base (G) when G binds. The emission of the fluorophore decreases with decreasing distance to Pt. Metal nuclide radiopharmaceuticals contain a metal core and an inner ligating unit, usually having chelate rings. The development of the advantageous fac-[99mTc(CO)3(H2O)3]+ precursor has opened new directions for radiolabeling. The non-radioactive fac-[Re(CO)3(H2O)3]+ analogue is useful in understanding the chemistry of agents derived from the [99mTc(CO)3(H2O)3]+ species. To achieve a net neutral coordination unit in radiopharmaceuticals with a fac-M(CO)3+ core (M = Tc, Re), facially coordinated monoanionic tridentate ligands (L-) are needed. Several fac-[Re(CO)3L] complexes containing the sulfonamido group as one terminal ligating group were synthesized and characterized by X-ray crystallography and NMR spectroscopy. For most sulfonamido complexes studied here, the two chelate rings have different pucker chirality, as is commonly found for a broad range of metal complexes. The complexes are stable at neutral and basic pH values and thus have potential for providing a neutral label in radiopharmaceuticals. The NMR signal averaging indicates that the rotations about the N-S and S-C bonds of the sulfonamido group are rapid on the NMR time scale. Understanding the chemical features of the prototypical complexes by using the fac-[Re(CO)3L]-analogue approach and the minimal ligand was the goal of this part of this investigation. fac-[Re(CO)3L]+ complexes containing prototypical NNN or NSN tridentate ligands, such as diethylenetriamine (dien) and simple dien derivatives, were investigated by X-ray crystallographic and NMR methods. fac-[Re(CO)3L]+ complexes with two terminal exo-NH groups exhibit unusually upfield exo-NH NMR signals, which shift downfield on addition of Cl- indicating 1:1 ion pairs forms involving one Cl- to two exo-NH's H-bonds.","abstract_html":"Platinum is the metal present in various classes of inorganic medicinal agents directed at important diseases such as cancer or viral infections. Several new Pt(II) complexes of polyamine ligands bearing a dansyl moiety linked by a sulfonamide group were prepared; in some cases the sulfonamide nitrogen formed a bond to Pt. The sulfonamido group donates strongly to Pt and places the dansyl group close to a vacant coordination position, allowing it to stack with bound guanine base (G) when G binds. The emission of the fluorophore decreases with decreasing distance to Pt. Metal nuclide radiopharmaceuticals contain a metal core and an inner ligating unit, usually having chelate rings. The development of the advantageous fac-[<sup>99m</sup>Tc(CO)<sub>3</sub>(H<sub>2</sub>O)<sub>3</sub>]<sup>+</sup> precursor has opened new directions for radiolabeling. The non-radioactive fac-[Re(CO)<sub>3</sub>(H<sub>2</sub>O)<sub>3</sub>]<sup>+</sup> analogue is useful in understanding the chemistry of agents derived from the [<sup>99m</sup>Tc(CO)<sub>3</sub>(H<sub>2</sub>O)<sub>3</sub>]<sup>+</sup> species. To achieve a net neutral coordination unit in radiopharmaceuticals with a fac-M(CO)<sub>3</sub><sup>+</sup> core (M = Tc, Re), facially coordinated monoanionic tridentate ligands (L<sup>-</sup>) are needed. Several fac-[Re(CO)<sub>3</sub>L] complexes containing the sulfonamido group as one terminal ligating group were synthesized and characterized by X-ray crystallography and NMR spectroscopy. For most sulfonamido complexes studied here, the two chelate rings have different pucker chirality, as is commonly found for a broad range of metal complexes. The complexes are stable at neutral and basic pH values and thus have potential for providing a neutral label in radiopharmaceuticals. The NMR signal averaging indicates that the rotations about the N-S and S-C bonds of the sulfonamido group are rapid on the NMR time scale. Understanding the chemical features of the prototypical complexes by using the fac-[Re(CO)<sub>3</sub>L]-analogue approach and the minimal ligand was the goal of this part of this investigation. fac-[Re(CO)<sub>3</sub>L]<sup>+</sup> complexes containing prototypical NNN or NSN tridentate ligands, such as diethylenetriamine (dien) and simple dien derivatives, were investigated by X-ray crystallographic and NMR methods. fac-[Re(CO)<sub>3</sub>L]<sup>+</sup> complexes with two terminal exo-NH groups exhibit unusually upfield exo-NH NMR signals, which shift downfield on addition of Cl<sup>-</sup> indicating 1:1 ion pairs forms involving one Cl<sup>-</sup> to two exo-NH's H-bonds.","abstract_has_math":false,"creators":["Christoforou, Anna Maria"],"institution":"Chemistry","degree_name":"Doctor of Philosophy (PhD)","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2007,"date_issued":"2007-01-01T08:00:00Z","date_published":"2007-01-01T08:00:00Z","updated_at":"2026-07-24T02:59:31Z","subjects":["rhenium tricarbonyl","platinum","sulfonamide ligands"],"languages":[],"rights":["restricted","Student has submitted appropriate documentation to restrict access to LSU for 365 days after which the document will be released for worldwide access."],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["etd-07112007-142442","https://repository.lsu.edu/gradschool_dissertations/1436"],"render_values":[{"text":"etd-07112007-142442","href":null,"code":true},{"text":"https://repository.lsu.edu/gradschool_dissertations/1436","href":"https://repository.lsu.edu/gradschool_dissertations/1436","code":true}]}]},"links":{"outbound_url":"https://doi.org/10.31390/gradschool_dissertations.1436","outbound_label":"DOI","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Christoforou, Anna Maria"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2007-07-09"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2022-05-12T23:12:07Z"]},{"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":["Doctor of Philosophy (PhD)"]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["Chemistry"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["rhenium tricarbonyl","platinum","sulfonamide ligands"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:rights","label":"Dc Rights","values":["restricted","Student has submitted appropriate documentation to restrict access to LSU for 365 days after which the document will be released for worldwide access."]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["etd-07112007-142442","10.31390/gradschool_dissertations.1436","https://repository.lsu.edu/gradschool_dissertations/1436"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["Platinum is the metal present in various classes of inorganic medicinal agents directed at important diseases such as cancer or viral infections. Several new Pt(II) complexes of polyamine ligands bearing a dansyl moiety linked by a sulfonamide group were prepared; in some cases the sulfonamide nitrogen formed a bond to Pt. The sulfonamido group donates strongly to Pt and places the dansyl group close to a vacant coordination position, allowing it to stack with bound guanine base (G) when G binds. The emission of the fluorophore decreases with decreasing distance to Pt. Metal nuclide radiopharmaceuticals contain a metal core and an inner ligating unit, usually having chelate rings. The development of the advantageous fac-[99mTc(CO)3(H2O)3]+ precursor has opened new directions for radiolabeling. The non-radioactive fac-[Re(CO)3(H2O)3]+ analogue is useful in understanding the chemistry of agents derived from the [99mTc(CO)3(H2O)3]+ species. To achieve a net neutral coordination unit in radiopharmaceuticals with a fac-M(CO)3+ core (M = Tc, Re), facially coordinated monoanionic tridentate ligands (L-) are needed. Several fac-[Re(CO)3L] complexes containing the sulfonamido group as one terminal ligating group were synthesized and characterized by X-ray crystallography and NMR spectroscopy. For most sulfonamido complexes studied here, the two chelate rings have different pucker chirality, as is commonly found for a broad range of metal complexes. The complexes are stable at neutral and basic pH values and thus have potential for providing a neutral label in radiopharmaceuticals. The NMR signal averaging indicates that the rotations about the N-S and S-C bonds of the sulfonamido group are rapid on the NMR time scale. Understanding the chemical features of the prototypical complexes by using the fac-[Re(CO)3L]-analogue approach and the minimal ligand was the goal of this part of this investigation. fac-[Re(CO)3L]+ complexes containing prototypical NNN or NSN tridentate ligands, such as diethylenetriamine (dien) and simple dien derivatives, were investigated by X-ray crystallographic and NMR methods. fac-[Re(CO)3L]+ complexes with two terminal exo-NH groups exhibit unusually upfield exo-NH NMR signals, which shift downfield on addition of Cl- indicating 1:1 ion pairs forms involving one Cl- to two exo-NH's H-bonds."]},{"key":"dc:title","label":"Title","values":["Exploring the binding of amine and sulfonamide ligands in Rhenium(I) Tricarbonyl and Platinum(II) complexes"]}]}],"canonical_facts":{"dc:creator":["Christoforou, Anna Maria"],"dc:date":["2007-07-09"],"dc:date.available":["2022-05-12T23:12:07Z"],"dc:description.abstract":["Platinum is the metal present in various classes of inorganic medicinal agents directed at important diseases such as cancer or viral infections. Several new Pt(II) complexes of polyamine ligands bearing a dansyl moiety linked by a sulfonamide group were prepared; in some cases the sulfonamide nitrogen formed a bond to Pt. The sulfonamido group donates strongly to Pt and places the dansyl group close to a vacant coordination position, allowing it to stack with bound guanine base (G) when G binds. The emission of the fluorophore decreases with decreasing distance to Pt. Metal nuclide radiopharmaceuticals contain a metal core and an inner ligating unit, usually having chelate rings. The development of the advantageous fac-[99mTc(CO)3(H2O)3]+ precursor has opened new directions for radiolabeling. The non-radioactive fac-[Re(CO)3(H2O)3]+ analogue is useful in understanding the chemistry of agents derived from the [99mTc(CO)3(H2O)3]+ species. To achieve a net neutral coordination unit in radiopharmaceuticals with a fac-M(CO)3+ core (M = Tc, Re), facially coordinated monoanionic tridentate ligands (L-) are needed. Several fac-[Re(CO)3L] complexes containing the sulfonamido group as one terminal ligating group were synthesized and characterized by X-ray crystallography and NMR spectroscopy. For most sulfonamido complexes studied here, the two chelate rings have different pucker chirality, as is commonly found for a broad range of metal complexes. The complexes are stable at neutral and basic pH values and thus have potential for providing a neutral label in radiopharmaceuticals. The NMR signal averaging indicates that the rotations about the N-S and S-C bonds of the sulfonamido group are rapid on the NMR time scale. Understanding the chemical features of the prototypical complexes by using the fac-[Re(CO)3L]-analogue approach and the minimal ligand was the goal of this part of this investigation. fac-[Re(CO)3L]+ complexes containing prototypical NNN or NSN tridentate ligands, such as diethylenetriamine (dien) and simple dien derivatives, were investigated by X-ray crystallographic and NMR methods. fac-[Re(CO)3L]+ complexes with two terminal exo-NH groups exhibit unusually upfield exo-NH NMR signals, which shift downfield on addition of Cl- indicating 1:1 ion pairs forms involving one Cl- to two exo-NH's H-bonds."],"dc:identifier":["etd-07112007-142442","10.31390/gradschool_dissertations.1436","https://repository.lsu.edu/gradschool_dissertations/1436"],"dc:rights":["restricted","Student has submitted appropriate documentation to restrict access to LSU for 365 days after which the document will be released for worldwide access."],"dc:subject":["rhenium tricarbonyl","platinum","sulfonamide ligands"],"dc:title":["Exploring the binding of amine and sulfonamide ligands in Rhenium(I) Tricarbonyl and Platinum(II) complexes"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Dissertation"],"thesis:degree_name":["Doctor of Philosophy (PhD)"],"thesis:institution_name":["Chemistry"]},"updated_at":"2026-07-24T02:59:31Z"}