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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

Electronic, Structural, and Catalytic Analyses of Iron Pincer Complexes and Methods for the Direct Functionalization of Lactide

Mako, Teresa Louise January 2017 (has links)
Thesis advisor: Amir Hoveyda / Chapter 1: A review of recent iron catalyzed cross coupling advances. Abstract: Herein, advances in iron catalyzed cross coupling from 2010-2015 are thoroughly reviewed. Newly developed protocols and the mechanistic work that has been conducted to gain understanding of these systems are discussed. Specific emphasis is placed on the techniques used for mechanistic investigations. Chapter 2: Cross coupling applications of pyridyl(diimine) iron complexes. Abstract: Versatile and redox noninnocent pyridyl(diimine) iron complexes were explored for catalytic ability in iron catalyzed cross coupling reactions. These complexes were found active for the coupling of benzyl halides and aryl Grignard reagents, producing moderate yields. Although active for the coupling of cyclohexyl chloride and aryl Grignard reagents, the catalytic ability of these complexes was not general for alkyl halides, and the majority of substrates readily underwent β- hydride elimination. Mechanistic studies indicated the role of PDIFe(I)Ph and PDIFe(0)(N2)2 as offcycle species. Additionally, these complexes were employed for the Suzuki-type coupling of alkyl halides with 1,1-bis(boronates), leading to the conclusion that the processes were instead base catalyzed. Chapter 3: Electronic structure analysis and catalytic applications of carbeno(diamidine) iron complexes. Abstract: Iron(II) pincer complexes carbeno(diamidine) iron dibromide [(CDA)FeBr2] and bis(N-heterocyclic carbene)pyridine iron dibromide [(CNC)FeBr2] were examined by magnetic circular dichroism and density functional theory studies to invesitgate the effect that NHC moieties have on electronic structure and bonding in tridentate pincer ligands. The increased Fe-C bonding and pincer-donating abilities that result from NHC incorporation have a direct impact on spin state and observed ligand fields. Additionally, the position of the NHC moiety on the tridentate ligand and the overall geometry of the molecule were found to effect the net donor ability of the pincers and the strength of the iron-pincer interactions. Three new variations of the CDA ligand were developed and evaluated for catalytic ability in olefin hydrogenation and atom transfer radical polymerization reactions. While iron CDA complexes were found to be mediocre catalysts for both transformations, a cobalt CDA dimer complex was developed that showed promising catalytic activity for olefin hydrogenation. Chapter 4: The direct functionalization of lactide. Abstract: In an effort to provide cyclic diesters that could generate useful and biodegradable polymers, the direct functionalization of lactide was pursued. Lactide undergoes ring opening under a wide range of conditions, and thus traditional methods used for the functionalization of lactones could not be employed here. Typical routes for the formation of cyclic diesters involve multi-step syntheses and low yielding cyclization reactions. Herein, C-H activation and soft enolization have been identified as promising avenues toward the direct functionalization of lactide. Palladium catalyzed C-H activation was not amenable for lactide, however, soft enolization techniques led to low yields of the desired functionalized product. / Thesis (MS) — Boston College, 2017. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

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