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Cover for Beta-Diketiminato Copper Complexes for C-H Bond Functionalization
dc.contributor.advisorWarren, Timothy Hen
dc.creatoren
dc.date.accessioned2014-08-15T15:05:53Zen
dc.date.created2014en
dc.date.issueden
dc.date.submitted01/01/2014en
dc.identifier.otherAPT-BAG: georgetown.edu.10822_709729.tar;APT-ETAG: 16885aa3798febf6ca6c72ad47dd2153en
dc.identifier.urien
dc.descriptionPh.D.en
dc.description.abstractC-H amination is an attractive methodology for constructing C-N bonds from seemingly unreactive C-H bonds. This process reduces group manipulations and reaction by-products. C-H amination catalysts are usually rhodium and ruthenium-based, though many catalysts are developing based on more Earth abundant, less toxic metals (e.g. copper). Generally, these catalytic systems imply metal nitrene [M]=NR as intermediate, typically generated through iminoiodinane PhI=NR as nitrene source. This limits the amino group into electron poor moieties like N-sulfonyls or N-carbamoyls. Organoazides N3R represent underutilized nitrene sources, which allows variable amino groups (N-alkyl, N-aryl, N-sulfonyl, N-phosphoryl, etc.) with N2 as stoichiometric by-product. These [M]=NR species are proposed to either (a) concertedly insert the NR group into a C-H bond or (b) abstract a hydrogen atom (HAA) to produce a carbon-based radical and a metal amido species, which later captures the carbon-based radical (RC). The ability to observe, isolate and characterize these intermediates leads to development of more efficient and selective catalytic protocols.en
dc.description.abstractThis thesis centers on beta-diketiminato copper catalyzed C-H amination using organoazides as nitrene sources. Mechanistic studies employing the isolable intermediate dicopper alkylnitrene {[Cl2NN]Cu}2(mu-NtBu) establishes the intermediacy of terminal copper nitrene [Cl2NN]Cu=NtBu in C-H amination via HAA / RC. Organoazide scope is explored including primary, secondary and tertiary alkylazides and arylazides. Experiments show intramolecular alpha-H migration and diazene formation as competing reactions involving copper nitrenes.en
dc.description.abstractThe reactivity of [Cl2NN]Cu=NR (R = 1-adamantyl or tert-butyl) towards unactivated C-H bond is investigated. Amination is generally favored at the weaker tertiary or secondary C-H bonds. Copper nitrene [Cu]=NR may also be employed as HAA reagent for functionalizing C-H bonds with functional groups (FG) other than the [Cu]-NHR that results from HAA. Stoichiometric and catalytic reactions of {[Cl2NN]Cu}2(mu-NR) and [Cl2NN]CuII-FG (FG = N-aryl, nitromethyl, phenoxy) in ethybenzene result to new C-FG bonds.en
dc.description.abstractSince nitrene (-NR) and oxo (-O) functionalities are isoelectronic, the chemistry of dicopper oxo species [Cu]2(mu-O) is also surveyed. Isolation of linked beta-diketiminato dicopper(I) complexes is presented. Through these dicopper(I) complexes, the cooperative nature of two copper centers in activating small molecules such as dioxygen, peroxides and azides is explored in initial reactivity studies.en
dc.formatPDFen
dc.format.extent281 leavesen
dc.languageenen
dc.publisherGeorgetown Universityen
dc.sourceGeorgetown University-Graduate School of Arts & Sciencesen
dc.sourceChemistryen
dc.subjectbeta-diketiminato copper complexen
dc.subjectcatalysisen
dc.subjectCH aminationen
dc.subjectCH bond functionalizationen
dc.subjectcopper nitreneen
dc.subject.lcshChemistryen
dc.subject.lcshChemistry, Inorganicen
dc.subject.otherChemistryen
dc.subject.otherInorganic chemistryen
dc.titleBeta-Diketiminato Copper Complexes for C-H Bond Functionalizationen
dc.typethesisen
gu.embargo.lift-date2016-08-15en
gu.embargo.terms2-yearsen


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