Coordination Chemistry of Bis(diphenylphosphino)amine Ligands with Cobalt Carbonyl and the Intermolecular Catalyzed Pauson-Khand Reaction

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dc.contributor.authorMerrill, James Malcolmen
dc.contributor.committeechairHanson, Brian E.en
dc.contributor.committeememberDeck, Paul A.en
dc.contributor.committeememberDillard, John G.en
dc.contributor.departmentChemistryen
dc.date.accessioned2014-03-14T20:30:20Zen
dc.date.adate2002-01-11en
dc.date.available2014-03-14T20:30:20Zen
dc.date.issued2001-12-19en
dc.date.rdate2003-01-11en
dc.date.sdate2002-01-10en
dc.description.abstractBis(diphenylphosphino)amine (PNP) ligands, prepared from (S)-(-)-1-methylbenzyl amine, (-)-cis-myrtanylamine, (S)-(-)-1,1-napthyl(ethyl)amine (PNP1 1a, PNP2 1b, and PNP3 1c respectively) and their cobalt carbonyl complexes are reported. In the absence of alkynes the PNP ligands chelate to the cobalt rather than bridging the two cobalt centers. Although the PNP ligands are chiral the crystal structures are best solved in centrosymmetric space groups with disorder at the chiral carbon with the exception of (PNP3)Co2(CO)6, 2c, which is solved in a non-centrosymmetric space group. When the PNP ligand chelates to cobalt, as in 2, the compounds show activity for the catalytic Pauson-Khand reaction, whereas when the PNP ligand bridges, as in 3, the reaction precedes stiochiometrically. The use of these chiral ligands has not yet resulted in enantioselective catalytic Pauson-Khand cycloadditions. However, a small 15% e.e. was detected for the stiochiometric Pauson-Khand cycloaddition with 3c as the metal substrate.en
dc.description.degreeMaster of Scienceen
dc.identifier.otheretd-01102002-163336en
dc.identifier.sourceurlhttp://scholar.lib.vt.edu/theses/available/etd-01102002-163336/en
dc.identifier.urihttp://hdl.handle.net/10919/30874en
dc.publisherVirginia Techen
dc.relation.haspartJamesMerrillmastersthesis.pdfen
dc.rightsIn Copyrighten
dc.rights.urihttp://rightsstatements.org/vocab/InC/1.0/en
dc.subjectphosphine ligandsen
dc.subjectasymmetricen
dc.subjecthomogeneous catalysisen
dc.subjectPauson-Khanden
dc.titleCoordination Chemistry of Bis(diphenylphosphino)amine Ligands with Cobalt Carbonyl and the Intermolecular Catalyzed Pauson-Khand Reactionen
dc.typeThesisen
thesis.degree.disciplineChemistryen
thesis.degree.grantorVirginia Polytechnic Institute and State Universityen
thesis.degree.levelmastersen
thesis.degree.nameMaster of Scienceen

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