Atom transfer reactions of high-valent chromium and manganese porphyrins

dc.contributor.advisor L. Keith Woo Goll, James
dc.contributor.department Chemistry 2018-08-15T04:53:21.000 2020-06-30T07:01:30Z 2020-06-30T07:01:30Z Tue Jan 01 00:00:00 UTC 1991 1991
dc.description.abstract <p>The terminally bound nitrido ligand of manganese(V) porphyrin complexes serves as a good bridging species in electron transfer processes. Thus, the nitrogen atom of a porphyrinatomanganese nitrido complex was reversibly transferred to porphyrinatomanganese(II), in a formal three-electron redox process. Evidence is presented that supports an inner-sphere mechanism for this process. The coordinating solvent, tetrahydrofuran, decreased the rate constant for this reaction by three orders of magnitude compared to that observed in the noncoordinating solvent, toluene. The number of redox equivalents exchanged in nitrogen atom transfer processes can be varied from three to two by choosing the appropriate reductant such as a porphyrinatomanganese(III) chloride complex. Evidence is presented to support a mechanism for the reaction between porphyrinatomanganese nitride and porphyrinatomanganese chloride which involves prior dissociation of the chloride ion before the formation of a [mu]-nitrido species. Thus when given a choice of potential bridging ligands (eg. N vs Cl or pivalate) the multi-electron process studied here preferentially selects the nitrido ligand;The terminally bound oxo ligand of chromium porphyrin complexes has also been shown to also serve as a good bridging ligand in electron transfer processes. It was demonstrated that a one-electron transfer involving complete atom transfer was possible by choosing the correct redox partner, a porphyrinatochromium(III) complex. The mechanism for this reaction has been shown to proceed through a [mu]-oxo species. Unlike the mechanism for porphyrinatomanganese chloride, the porphyrinatochromium chloride complex does not require prior dissociation of the chloride ion. The rate constant was not decreased by addition of a ten fold excess of chloride ion.</p>
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dc.identifier archive/
dc.identifier.articleid 11034
dc.identifier.contextkey 6384999
dc.identifier.s3bucket isulib-bepress-aws-west
dc.identifier.submissionpath rtd/10035
dc.language.iso en
dc.source.bitstream archive/|||Fri Jan 14 18:12:27 UTC 2022
dc.subject.disciplines Inorganic Chemistry
dc.subject.keywords Chemistry
dc.subject.keywords Inorganic chemistry
dc.title Atom transfer reactions of high-valent chromium and manganese porphyrins
dc.type article
dc.type.genre dissertation
dspace.entity.type Publication
relation.isOrgUnitOfPublication 42864f6e-7a3d-4be3-8b5a-0ae3c3830a11 dissertation Doctor of Philosophy
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