Oxidative addition of N-H and O-H bonds to iridium: developing active catalysts for N-H and O-H additions to unsaturates

dc.contributor.authorLapido, Folami Tesileemen
dc.contributor.committeechairMerola, Joseph S.en
dc.contributor.committeememberHanson, Brian E.en
dc.contributor.committeememberDillard, John G.en
dc.contributor.committeememberTanko, James M.en
dc.contributor.committeememberGibson, Harry W.en
dc.contributor.departmentChemistryen
dc.date.accessioned2014-03-14T21:21:06Zen
dc.date.adate2005-10-13en
dc.date.available2014-03-14T21:21:06Zen
dc.date.issued1991-07-05en
dc.date.rdate2005-10-13en
dc.date.sdate2005-10-13en
dc.description.abstractThe oxidative addition of the N-H bond of both heterocyclic and acyclic amines and the O-H bond of phenols, water and carboxylic acids to iridium(I) trimethylphosphines complexes was studied and the reactivity of the resulting hydrido amido-, aryloxo- and carboxylato iridium(III) complexes was investigated. Oxidative addition of the N-H bond of pyrrole, indole, 3-methylindole, 7-azaindole, carbazole and aniline to [Ir(COD)(PMe₃)₃]CI (<b>1a</b>) (COD = 1,5-cyclooctadiene) produces merIr( NR₂)H(PMe₃)₃CI (<b>2a-f</b>) complexes. That these amines were bound to iridium through an Ir-N bond was established by ¹H, ³¹P and ¹³C NMR spectroscopy, IR spectroscopy, C-H analyses and single crystal x-ray diffraction. Similarly, oxidative addition of the O-H bond of phenol, p-cresol, 3,5-dimethylphenol, and water to [Ir(COD)(PMe₃)₃]CI (la) produces mer-Ir(OR)H(PMe₃)₃C1 (<b>5a-c and 6</b>) which were characterized by ¹H, ³¹P and ¹³C NMR spectroscopy, C H analyses and single crystal x-ray diffraction. A preliminary study of the reactivity of both the amido and aryloxo complexes suggests that because of the increased electron affinity of the heteroatoms involved (N or 0), there is high electron density at the heteroatoms in these complexes and therefore the M-N or M-O bond can heterolyze more easily than M-C bonds. This increased tendency of the M-N or M-O bond to heterolyze leads to decomposition reactions when attempts are made to open up a coordination site at the metal center by removing the chloride ligand.en
dc.description.degreePh. D.en
dc.format.extentxi, 229 leavesen
dc.format.mediumBTDen
dc.format.mimetypeapplication/pdfen
dc.identifier.otheretd-10132005-152537en
dc.identifier.sourceurlhttp://scholar.lib.vt.edu/theses/available/etd-10132005-152537/en
dc.identifier.urihttp://hdl.handle.net/10919/39829en
dc.language.isoenen
dc.publisherVirginia Techen
dc.relation.haspartLD5655.V856_1991.L3685.pdfen
dc.relation.isformatofOCLC# 24990638en
dc.rightsIn Copyrighten
dc.rights.urihttp://rightsstatements.org/vocab/InC/1.0/en
dc.subject.lccLD5655.V856 1991.L3685en
dc.subject.lcshIridium catalystsen
dc.subject.lcshIridiumen
dc.titleOxidative addition of N-H and O-H bonds to iridium: developing active catalysts for N-H and O-H additions to unsaturatesen
dc.typeDissertationen
dc.type.dcmitypeTexten
thesis.degree.disciplineChemistryen
thesis.degree.grantorVirginia Polytechnic Institute and State Universityen
thesis.degree.leveldoctoralen
thesis.degree.namePh. D.en

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