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Structural Design and Catalytic Applications of Homogenous and Heterogeneous Organometallic Lewis Acids

Reiner, Benjamin Russell

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2018, Doctor of Philosophy, Ohio State University, Chemistry.
A broad goal of organometallic chemistry to use ligand and catalyst design to effect useful chemical transformations. Rational design of novel ligands has allowed us to study how binuclear, redox active, or supramolecular frameworks can engender new or enhanced chemical reactivity. One of the major barriers to adopting gold into traditional two electron redox cycling is the high potential required to access gold(III). Use of a binuclear gold framework can eschew this issue by distributing the redox load over multiple metal sites. Phosphorus ylide gold dimers support a wide range of oxidation states which has allowed study into the reductive processes involved in the thermolysis of arylated or alkylated gold(III,III) complexes. Additionally, the binuclear framework allows access to a dicationic gold(II,II) complex that exhibits markedly superior Lewis acid mediated catalytic activity compared to gold complexes supported by other ligands or in other oxidation states. While rylene imides have a variety of applications in electrical energy storage devices, their use as redox non-innocent ligands has been severely underexplored. Rigorous electrochemical and photochemical investigations have shown how reduced naphthalene diimide (NDI) species interact with charge dense redox inactive cations such as Mg2+ or Li+. Moreover, chemical reduction revealed formation of a discrete dimeric complex that features strong coordination of the NDI oxygen atoms to the Mg centers. Electrochemical and structural studies into the interaction between rylene imides and transition metals was accomplished by using NDI or phthalimide ligands decorated with pyridyl-thiazole units. Cyclic voltammetry of the ensuing Co2+ and Zn2+ complexes uncovered important structure function relationships between the redox state of the ligand and the accessibility of metal-borne reduction events. Metal-organic frameworks (MOFs) are a hybrid class of material which allow translation of well-established principles in homogenous catalysis into a heterogenous context. Diphosphine pincer complexes facilitate a multitude of impressive catalytic processes but can suffer from deactivation processes that limit their long term activity. Immobilization of diphosphine pincer complexes as linkers within MOFs can extend catalytic lifetime by suppressing deleterious side reactions. Lattice immobilized Pd PNNNP (PNNNP = 2,6-(HNPAr2)2C5H3N; Ar = p-C6H4CO2-) pincer complexes demonstrate longer catalytic lifetimes in Lewis acid mediated catalysis compared to homogenous analogs. Additionally, immobilized Pd PNNNP pincer complexes were found to exhibit size selective catalytic activity which was not for a homogenous analog.
Casey Wade, Prof. (Advisor)
Hannah Shafaat, Prof. (Committee Member)
Christo Sevov, Prof. (Committee Member)
Trisha Van Zandt, Prof. (Committee Member)
219 p.

Recommended Citations

Citations

  • Reiner, B. R. (2018). Structural Design and Catalytic Applications of Homogenous and Heterogeneous Organometallic Lewis Acids [Doctoral dissertation, Ohio State University]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=osu1534687723695723

    APA Style (7th edition)

  • Reiner, Benjamin. Structural Design and Catalytic Applications of Homogenous and Heterogeneous Organometallic Lewis Acids. 2018. Ohio State University, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=osu1534687723695723.

    MLA Style (8th edition)

  • Reiner, Benjamin. "Structural Design and Catalytic Applications of Homogenous and Heterogeneous Organometallic Lewis Acids." Doctoral dissertation, Ohio State University, 2018. http://rave.ohiolink.edu/etdc/view?acc_num=osu1534687723695723

    Chicago Manual of Style (17th edition)