Oxidation addition of H-H bonds to iridium: developing novel active water soluble catalysts for hydrogenation of unsaturates
dc.contributor.author | Le, Trang X. | en |
dc.contributor.committeechair | Merola, Joseph S. | en |
dc.contributor.committeemember | Hanson, Brian E. | en |
dc.contributor.committeemember | Dillard, John G. | en |
dc.contributor.committeemember | Tanko, James M. | en |
dc.contributor.committeemember | Anderson, Mark R. | en |
dc.contributor.department | Chemistry | en |
dc.date.accessioned | 2014-03-14T21:19:14Z | en |
dc.date.adate | 2008-09-23 | en |
dc.date.available | 2014-03-14T21:19:14Z | en |
dc.date.issued | 1992-08-05 | en |
dc.date.rdate | 2008-09-23 | en |
dc.date.sdate | 2008-09-23 | en |
dc.description.abstract | The 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.degree | Ph. D. | en |
dc.format.extent | ix, 227 leaves | en |
dc.format.medium | BTD | en |
dc.format.mimetype | application/pdf | en |
dc.identifier.other | etd-09232008-144717 | en |
dc.identifier.sourceurl | http://scholar.lib.vt.edu/theses/available/etd-09232008-144717/ | en |
dc.identifier.uri | http://hdl.handle.net/10919/39462 | en |
dc.language.iso | en | en |
dc.publisher | Virginia Tech | en |
dc.relation.haspart | LD5655.V856_1992.L4.pdf | en |
dc.relation.isformatof | OCLC# 27859490 | en |
dc.rights | In Copyright | en |
dc.rights.uri | http://rightsstatements.org/vocab/InC/1.0/ | en |
dc.subject.lcc | LD5655.V856 1992.L4 | en |
dc.subject.lcsh | Iridium catalysts | en |
dc.subject.lcsh | Oxidizing agents | en |
dc.title | Oxidation addition of H-H bonds to iridium: developing novel active water soluble catalysts for hydrogenation of unsaturates | en |
dc.type | Dissertation | en |
dc.type.dcmitype | Text | en |
thesis.degree.discipline | Chemistry | en |
thesis.degree.grantor | Virginia Polytechnic Institute and State University | en |
thesis.degree.level | doctoral | en |
thesis.degree.name | Ph. D. | en |
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