Inorganic Chemistry Commons^™

Design And Synthesis Of Novel Octacarboxy Porphyrinic Metal-Organic Frameworks, Jacob A. Johnson

Department of Chemistry: Dissertations, Theses, and Student Research

Metal-Organic Frameworks (MOFs) are a class of nanoporous crystalline materials constructed via the interconnection between metal-ions/inorganic clusters and organic ligands. Since the surface area, pore size and distribution, and chemical functionalities of MOFs are highly tunable via the judicious combinations of inorganic clusters and organic ligands, MOFs have attracted intensive interests for a variety of applications including gas adsorption and separation, catalysis, chemical sensing, and drug delivery among others. Porphyrin based ligands are of particular interest for building functional MOFs due to their unique photo-, electro-, and catalytic properties. In addition, the four-fold symmetry of porphyrin ligands offers an effective …

Visible-Light Generation Of High-Valent Metal-Oxo Intermediates And A Biomimetic Oxidation Catalyzed By Manganese Porphyrins With Iodobenzene Diacetate, Ka Wai Kwong

Masters Theses & Specialist Projects

High-valent iron-oxo intermediates play central roles as active oxidants in enzymatic and synthetic catalytic oxidations. Many transition metal catalysts are designed for biomimetic studies of the predominant oxidation catalysts in Nature, the cytochrome P450 enzymes.

In this work, a new photochemical method to generate high-valent iron-oxo porphyrin models was discovered. As controlled by the electronic nature of porphyrin ligands, iron(IV)-oxo porphyrin radical cations (Compound I model) and iron(IV)-oxo porphyrin derivatives (Compound II model) were produced. These observations indicate that the photochemical reactions involve a heterolytic cleavage of O-Br in precursors to give a putative iron(V)-oxo intermediate, which might relax to …

Mida Boronates Are Hydrolysed Fast And Slow By Two Different Mechanisms, Jorge A. Gonzalez, O. Maduka Ogba, Gregory F. Morehouse, Nicholas Rosson, Kendall N. Houk, Andrew G. Leach, Paul H.-Y. Cheong, Martin D. Burke, Guy C. Lloyd-Jones

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

MIDA boronates (N-methylimidodiacetic boronic acid esters) serve as an increasingly general platform for building-block-based small molecule construction, largely due to the dramatic and general rate differences with which they are hydrolysed under various basic conditions. Yet the mechanistic underpinnings of these rate differences have remained unclear, hindering efforts to address current limitations of this chemistry. Here we show that there are two distinct mechanisms for this hydrolysis: one is base-mediated and the other neutral. The former can proceed more than three orders of magnitude faster, and involves rate-limiting attack at a MIDA carbonyl carbon by hydroxide. The alternative ‘neutral’ hydrolysis …

Synthesis And Characterization Of Organic-Inorganic Hybrid Materials For Thermoelectric Devices, Paige M. Huzyak

Masters Theses & Specialist Projects

The development of organic-inorganic hybrid materials is of great interest in thermoelectrics for its potential to combine the desirable characteristics of both classes of materials. Thermoelectric materials must combine low thermal conductivity with high electrical conductivity, but in most materials, thermal and electrical conductivity are closely related and positively correlated. By combining the low thermal conductivity, flexibility, facile processing, and low cost of organic components with the high electrical conductivity and stability of inorganic components, materials with beneficial thermoelectric properties may be realized.

Here, we describe the synthesis and characterization of anthracene-containing organic-inorganic hybrid materials for thermoelectric purposes. Specifically, POSS-ANT …

Decarbonylative Cross Coupling Of Phthalimides With Diorganozinc Reagents—Efforts Toward Catalysis, Kimberly S. Deglopper, Sarah K. Fodor, Thomas Bd Endean, Jeffrey B. Johnson

Faculty Publications

The decarbonylative coupling of phthalimides with diorganozinc reagents to form o-substituted benzamides has been previously demonstrated as a viable process, but only with stoichiometric nickel(0). Investigations into a number of reaction variables, including solvent, ligand, and substrate substitution, have yielded multiple sets of conditions capable of achieving up to 10 catalyst turnovers, most successfully with the use of electron withdrawing nitrogen substituents on the phthalimide. In addition, these investigations have provided insight into the intermediates within the catalytic cycle and have revealed new approaches to the development of a general catalytic methodology.