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Please use this identifier to cite or link to this item: http://hdl.handle.net/1903/12863

Title: REDUCTIVE ELIMINATION OF (DPMS)PTIV COMPLEXES DERIVED FROM ISOMERIC 2-BUTENEs AND 2-BUTYNE (DPMS=DI(2-PYRIDYL)METHANE SULFONATE)
Authors: Liu, Xiaohang
Advisors: Vedernikov, Andrei
Department/Program: Chemistry
Type: Thesis
Sponsors: Digital Repository at the University of Maryland
University of Maryland (College Park, Md.)
Subjects: Chemistry
Keywords: Alkene
Alkyne
Organometallics
Platinum
Issue Date: 2012
Abstract: The (dpms)PtII complexes (dpms = di(2-pyridinyl)methanesulfonate)derived from some cyclic olefins can be readily oxidized to PtIV oxetanes, followed by reductive elimination to produce corresponding epoxides. A catalytic version of this reaction can potentially be achieved if decomposition of active species responsible for olefin substitution is avoided. Several attempts were made to solve this problem, and a more hydrophilic analog of the dipyridinemethanesulfonate ligand was obtained. Furthermore, the reductive elimination step of PtIV oxetanes was studied by using diastereomeric cis- and trans-2-butene derivatives. We believe that two mechanisms of C O reductive elimination may be involved in these reactions and that steric repulsion between substituents at the oxetane carbon atoms may play a major role in determining the predominant of the two competing mechanisms. Platinum(IV) η1-butanone complex was synthesized and characterized, which was found to undergo different types of elimination reaction to give a series of butane derivatives as products.
URI: http://hdl.handle.net/1903/12863
Appears in Collections:UMD Theses and Dissertations
Chemistry & Biochemistry Theses and Dissertations

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