Attempted Synthesis of a 10-P-3 Species: Cyclization Interrupts the Pathway

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dc.contributor.advisorCain, Matthew
dc.contributor.authorChinen, Beatrice
dc.contributor.departmentChemistry
dc.date.accessioned2021-09-30T18:07:46Z
dc.date.available2021-09-30T18:07:46Z
dc.date.issued2021
dc.description.degreeM.S.
dc.identifier.urihttp://hdl.handle.net/10125/76340
dc.subjectChemistry
dc.titleAttempted Synthesis of a 10-P-3 Species: Cyclization Interrupts the Pathway
dc.typeThesis
dcterms.abstractMain group (MG) element-based catalysis provides an enticing solution to the health and environmental problems associated with traditional transition metal catalysis. However, a major obstacle is the large HOMO-LUMO gap present in MG compounds. Confining the active center in a geometrically-distorted rigid chelated structure has shown promise by lowering this barrier and enabling fundamental organometallic-type processes like oxidative addition, insertion, and reductive elimination, leading us to pursue the synthesis of 10-P-3 species 8. To that end, a modified procedure was developed to generate Martin ligand 7-Br, an electron-deficient diol. The ligand was methylated with MeI in the presence of K2CO3 affording diether 9, which was characterized by NMR spectroscopy, elemental analysis, and X-ray crystallography. We hypothesized that exposure of 9 to a three-step metal-halogen exchange/phosphination/reduction sequence would generate target 8, a hypervalent 10–P–3 species stabilized within a rigid pincer framework by electron-withdrawing axial O-donors. Instead, after phosphination, the presumed PCl2-substituted intermediate underwent cyclization to monochlorinated 10, which was functionalized to p-tolyl-substituted 11 and characterized by NMR spectroscopy, elemental analysis, and X-ray crystallography. This work provides insights into cyclization chemistry in fluorinated OCO pincer compounds that will guide future attempts at generating hypervalent 10-P-3 species.
dcterms.extent127 pages
dcterms.languageen
dcterms.publisherUniversity of Hawai'i at Manoa
dcterms.rightsAll UHM dissertations and theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission from the copyright owner.
dcterms.typeText
local.identifier.alturihttp://dissertations.umi.com/hawii:11138

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