Physical Sciences and Mathematics Commons^™

Hypervalent Iodine Compounds With Carboxylate And Tetrazolate Ligands, Avichal Vaish

Chemistry Theses and Dissertations

In modern organic chemistry, hypervalent (HV) iodine(III) compounds are frequently used as oxidizing agents but application of λ³-iodanes in polymer and material chemistry is still underexplored. This dissertation describes the preparation of dynamic and self-healing materials by employing ligand exchange reactions involving HV iodine(III) compounds of the type ArIL₂ (Ar = Aryl, L = ligand, e.g., carboxylate or (pseudo)halide). These compounds can undergo ligand exchange reactions in presence of nucleophiles (Nu^-) to form ArINu₂. Diacetoxyiodo benzene was successfully employed as a crosslinker to prepare dynamic and self-healing gels derived from carboxylate-containing polymers. Furthermore, …

Oxidative C–C And C–Heteroatom Reactivity Of High-Valent Nickel Complexes, Sofia Marie Smith

Arts & Sciences Electronic Theses and Dissertations

ABSTRACT OF THE DISSERTATION

Oxidative C–C and C–Heteroatom Reactivity of High-Valent Nickel Complexes

by

Sofia M. Smith

Doctor of Philosophy in Chemistry

Washington University in St. Louis, 2019

Professor Liviu M. Mirica, Chair

Professor Kevin D. Moeller, Co-Chair

Nickel catalysts are commonly used for cross-coupling reactions such as Negishi, Kumada and Suzuki couplings. While Ni(0), Ni(I), and Ni(II) intermediates are most relevant in these transformations, Ni(III) and Ni(IV) species have also been recently proposed to play a role in catalysis. The formation of C–C and C–heteroatom bonds plays a fundamental role in organic transformations, and today cross-coupling reactions are one …

Reactivity Of Molybdenum And Tungsten Sulfido Complexes With First-Series Transition Metals, Khalil Mudarmah

ETD Archive

Ammonium tetrathiomolybdate (ATTM) is an important compound in bioinorganic chemistry, with medicinal applications. Metal complexes of sulfur-containing ligands have been widely used as building block in biology and inorganic chemistry. This project aims to increase the number of Mo-S and W-S complexes that may contribute to fields such as bioinorganic and medicinal chemistry, by the preparation of heterometallic complexes containing both Mo or S and a metal of the first transition series. The homobimetallic complex anion salts (Et4N)2[Mo2(S)2(μ-S)2(edt)2] (1) and (Et4N)2[W2(S)2(μ-S)2(edt)2] (2) have been prepared from ATTM and ammonium tetrathiotungstate (ATTW) in order to start our work. The overnight treatment …

Synthesis And Adsorption Experiments With Metal-Organic Frameworks For High School And Undergraduate Laboratory Settings, Kate Holley

Legacy Theses & Dissertations (2009 - 2024)

Seven experiments are described and outlined here that introduce high school and undergraduate students to metal–organic frameworks (MOFs) and their applications. The experiments were designed to be completed with basic laboratory equipment and supplies and without the use of expensive characterization instruments, simulating typical high school chemistry laboratory conditions. Students synthesized two well-known MOFs, HKUST-1 and aluminum fumarate, using simple, safe, and rapid methods (fast enough to be performed within the time constrains of a typical high school class). Students then use their synthesized MOFs to explore their inherent sorption properties. In one set of experiments, the synthesized MOFs are …