Synthesis, characterization and reactivity of new nickel(II) complexes towards urea and carbon dioxide

dc.contributor.advisorMusie, Ghezai T.
dc.contributor.authorSeals, William
dc.contributor.committeeMemberWalmsley, Judith A.
dc.contributor.committeeMemberZhao, John Cong-Gui
dc.date.accessioned2024-02-12T20:02:16Z
dc.date.available2024-02-12T20:02:16Z
dc.date.issued2012
dc.descriptionThis item is available only to currently enrolled UTSA students, faculty or staff. To download, navigate to Log In in the top right-hand corner of this screen, then select Log in with my UTSA ID.
dc.description.abstractInspired by biological systems, the field of catalytic hydrolysis of small molecules such as urea and carbon dioxide by nickel(II) complexes has been actively pursued for several years. Few complexes with catalytic activity towards Thai-Micheal addition and carbon dioxide fixation have been reported in the literature, and they remain largely an unresolved issues. In an attempt to develop model catalysts that would hydrolyze urea and carbon dioxide, a dinucleating ligand N,N'-Bis[2-carboxybenzomethyl]-N,N'-Bis[carboxymethyl]-1,3-diaminopropan-2-ol, <bold>H<sub>5</sub>ccdp</bold> and its nickel(II) complexes have been synthesized and characterized. Under different reaction conditions and ligand to nickel(II) stoichiometric ratios, four new complexes have been synthesized. The complexes range from <italic>mono</italic>-nickel <bold>(K<sub>2</sub>[Ni(Hccdp)]<super>.</super>8H<sub>2</sub>O</bold> (<bold>K<sub>2</sub>[1]<super>.</super>8H<sub>2</sub>O</bold>) and <bold>Ni(H<sub>2</sub>O)<sub>6</sub>[Ni(Hccdp)(H<sub>2</sub>O)<sub>2</sub>]<sub>2</sub><super>.</super>12H<sub>2</sub>O</bold> (<bold>Ni(H<sub>2</sub>O)<sub>6</sub>[2]<sub>2</sub><super>.</super>12H<sub>2</sub>O</bold>) to the <italic>di</italic>-nickel <bold>(K<sub>2</sub>[Ni<sub>2</sub>(ccdp)(C<sub>5</sub>H<sub>7</sub>O<sub>2</sub>)(H<sub>2</sub>O)<sub>2</sub>]<super>.</super>7H<sub>2</sub>O</bold> (K<sub>2</sub>[3]<super>.</super>7H<sub>2</sub>O))</bold>, and <italic>tetra</italic>-nickel <bold>Cs<sub>6</sub>[Ni<sub>4</sub>(ccdp)<sub>2</sub>(µ-%eta;<super>2</super>-%eta;<super>2</super>-CO<sub>3</sub>)<sub>2</sub>]<super>.</super>23H<sub>2</sub>O</bold> (<bold>Cs<sub>6</sub>[4]*23H<sub>2</sub>O</bold>) in nuclearity. In these reactions, <bold>H<sub>5</sub>ccdp</bold> ligand has shown considerable flexibility in coordinating with nickel(II) ions to produce the complexes. The complexes have been characterized using Uv-Vis, IR, X-ray crystallography, mass spectroscopy and electrochemical techniques. Of the synthesized nickel complexes, the complex <bold>K<sub>2</sub>[3]<super>.</super>7H<sub>2</sub>O</bold> has shown activity towards carbon dioxide, urea and acetonitrile in basic aqueous media <italic>via</italic> a <italic>bis</italic>-<italic>µ</italic>-OH <italic>tetra</italic>-nickel reactive intermediate to produce the <bold>Cs<sub>6</sub>[4]<super>.</super>23H<sub>2</sub>O</bold> complex. In this thesis, a detailed discussion of the synthesis, characterization and reactivity of these nickel complexes and the <italic>in situ</italic> synthesized <bold>[Ni<sub>4</sub>(ccdp)<sub>2</sub>(µ-OH)<sub>2</sub>]<super>4-</super></bold> intermediate towards urea, carbon dioxide and acetonitrile is described.
dc.description.departmentChemistry
dc.format.extent75 pages
dc.format.mimetypeapplication/pdf
dc.identifier.isbn9781267615893
dc.identifier.urihttps://hdl.handle.net/20.500.12588/5311
dc.languageen
dc.subjectcarbon dioxide
dc.subjectNi(II) complexes
dc.subjecturease
dc.subject.classificationChemistry
dc.subject.classificationInorganic chemistry
dc.titleSynthesis, characterization and reactivity of new nickel(II) complexes towards urea and carbon dioxide
dc.typeThesis
dc.type.dcmiText
dcterms.accessRightspq_closed
thesis.degree.departmentChemistry
thesis.degree.grantorUniversity of Texas at San Antonio
thesis.degree.levelMasters
thesis.degree.nameMaster of Science

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