Oxidation addition of H-H bonds to iridium: developing novel active water soluble catalysts for hydrogenation of unsaturates

dc.contributor.authorLe, Trang X.en
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.committeememberAnderson, Mark R.en
dc.contributor.departmentChemistryen
dc.date.accessioned2014-03-14T21:19:14Zen
dc.date.adate2008-09-23en
dc.date.available2014-03-14T21:19:14Zen
dc.date.issued1992-08-05en
dc.date.rdate2008-09-23en
dc.date.sdate2008-09-23en
dc.description.abstractThe oxidative addition of H-H to iridium(l) trimethylphosphine complexes was studied and the reactivity of the resulting water soluble dihydrido iridium (III) complexes was investigated. One Dihydrido iridium(III) complex, mer-Ir(H)₂(PMe₃)₃CI <b>(2)</b> was characterized by ¹H, ³¹p and ¹³C NMR spectroscopy, CH analysis and single crystal xray diffraction. <b>(2)</b> reacted with the strong sigma donor PMe₃ to form [IrH2(PMe₃)4]CI <b>(3b)</b> without having to remove the chloride ligand. <b>(2)</b> reacted with monosubstituted acetylenes and an internal diyne in water to form the vinyl complexes Ir(H)(C(R')=C(H)-(R))(PMe₃)₃CI (R = CMe₃, C₆H₅, SiMe₃, R' = H, <b>(4)-(6);</b> R' = CCMe₃, R= Me, <b>(7)). (2)</b> also reacted in water with ethynylpyridine to form an unusual metallacycle "trimer" <b>(8)</b>. A mechanism for tltrimerizationtl is proposed. <b>(2)</b> also reacted with ethylene in water to form the diethyl iridium complex Ir(CH₂CH₃)₂(PMe₃)₃CI <b>(8)</b>. Encouraged by these results, catalytic hydrogenation of unsaturates in water was investigated. It was found that <b>(2)</b> is active as a water soluble catalyst for hydrogenation of unsaturates. A mechanism for catalytic hydrogenation was proposed.en
dc.description.degreePh. D.en
dc.format.extentix, 227 leavesen
dc.format.mediumBTDen
dc.format.mimetypeapplication/pdfen
dc.identifier.otheretd-09232008-144717en
dc.identifier.sourceurlhttp://scholar.lib.vt.edu/theses/available/etd-09232008-144717/en
dc.identifier.urihttp://hdl.handle.net/10919/39462en
dc.language.isoenen
dc.publisherVirginia Techen
dc.relation.haspartLD5655.V856_1992.L4.pdfen
dc.relation.isformatofOCLC# 27859490en
dc.rightsIn Copyrighten
dc.rights.urihttp://rightsstatements.org/vocab/InC/1.0/en
dc.subject.lccLD5655.V856 1992.L4en
dc.subject.lcshIridium catalystsen
dc.subject.lcshOxidizing agentsen
dc.titleOxidation addition of H-H bonds to iridium: developing novel active water soluble catalysts for hydrogenation of 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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