Chemistry & Biochemistry Theses and Dissertations

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REDUCTIVE ELIMINATION OF (DPMS)PTIV COMPLEXES DERIVED FROM ISOMERIC 2-BUTENEs AND 2-BUTYNE (DPMS=DI(2-PYRIDYL)METHANE SULFONATE)
(2012) Liu, Xiaohang; Vedernikov, Andrei; Chemistry; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)
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.