Novel Group 4, 9, 10, and 12 Complexes of Indenyl-Derived Ylides

dc.contributor.authorPurdavaie, Kouroshen
dc.contributor.departmentChemistryen
dc.contributor.supervisorBaird, Michael C.en
dc.date2015-06-01 00:14:55.56
dc.date.accessioned2015-06-02T17:58:09Z
dc.date.available2015-06-02T17:58:09Z
dc.date.issued2015-06-02
dc.degree.grantorQueen's University at Kingstonen
dc.descriptionThesis (Ph.D, Chemistry) -- Queen's University, 2015-06-01 00:14:55.56en
dc.description.abstractThe coordination chemistry of the phosphonium-1-indenylide (PHIN) ligand methyldiphenylphosphonium-1-indenylide (1-C9H6PMePh2, I) has been studied, and a new phosphonium-1-indenylide (PHIN) ligand methyldiphenylphosphonium-4,7-dimethyl-1-indenylide (4,7-dimethyl-1-C9H4PMePh2, II) has prepared and characterized by NMR spectroscopy, elemental analysis and X-ray crystallography. The zwitterionic structure of methyldiphenylphosphonium-4,7-dimethyl-1-indenylide II is isoelectronic with the cyclopentadienyl ligand and one can anticipate interesting coordination chemistry.[Ir(COD)][BF4] and [Rh(COD)][BF4] were prepared by reactions of silver tetrafluoroborate, AgBF4, with [Ir(COD)Cl]2 and [Rh(COD)Cl]2 and by reacting the resulting [Ir(COD)][BF4] and [Rh(COD)][BF4] with I and II. The resulting planar chiral iridium(I) and rhodium(I) complexes [Ir(η4-C8H12)(η5-I)]BF4 (III), [Ir(η4-C8H12)(η5-II)]BF4 (IV), [Rh(η4-C8H12)(η5-I)]BF4 (V), and [Rh(η4-C8H12)(η5-II)]BF4 (VI) were synthesized as pairs of enantiomers depending on which face of five-membered rings coordinates to the metal centers. The iridium and rhodium complexes have been characterized by extensive NMR spectroscopy, high resolution mass spectrometry and elemental analyses. Hydrogenation of [Rh(η4-C8H12)(η5-I)]BF4 (V) and the oxidative addition of methyl iodide and benzyl chloride to all the new complexes III-VI were attempted. Coordination of I to a variety of metals in Groups IV, IX, X, and XII, was attempted.en
dc.description.degreePhDen
dc.identifier.urihttp://hdl.handle.net/1974/13108
dc.language.isoengen
dc.relation.ispartofseriesCanadian thesesen
dc.rightsQueen's University's Thesis/Dissertation Non-Exclusive License for Deposit to QSpace and Library and Archives Canadaen
dc.rightsProQuest PhD and Master's Theses International Dissemination Agreementen
dc.rightsIntellectual Property Guidelines at Queen's Universityen
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dc.rightsCreative Commons - Attribution - CC BYen
dc.rightsThis publication is made available by the authority of the copyright owner solely for the purpose of private study and research and may not be copied or reproduced except as permitted by the copyright laws without written authority from the copyright owner.en
dc.subjectphosphonium-1-indenylide (PHIN)en
dc.subjectOrganometallicen
dc.subjectInorganicen
dc.titleNovel Group 4, 9, 10, and 12 Complexes of Indenyl-Derived Ylidesen
dc.typethesisen
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