Jenna A. Bilbrey

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The kinetic isotope effect (KIE) is used to experimentally elucidate the first irreversible step in oxidative addition reactions of a zerovalent nickel catalyst to a set of haloarene substrates. Halogenated o-methylbenzene, dimethoxybenzene, and thiophene derivatives undergo intramolecular oxidative addition through irreversible π-complexation. Density(More)
Palladium-mediated surface-initiated Kumada catalyst transfer polycondensation is used to generate poly(3-methyl thiophene) films with controlled thickness up to 100 nm. The palladium initiator density is measured using cyclic voltammetry and a ferrocene-capping agent, where the surface density is found to be 55% (1.1 × 10(14) molecules per cm(2)). UV-Vis(More)
Steric demands of a ligand can be quantified by the area occluded by the ligand on the surface of an encompassing sphere centered at the metal atom. When viewed as solid spheres illuminated by the metal center, the ligand atoms generally cast a very complicated collective shadow onto the encompassing sphere, causing mathematical difficulties in computing(More)
Many properties of transition-metal complexes depend on the steric bulk of bound ligands, usually quantified by the Tolman (θ) and solid (Θ) cone angles, which have proven utility but suffer from various limitations and coarse approximations. Here, we present an improved, mathematically rigorous method to determine an exact cone angle (θ°) by solving for(More)
This article reports the development of a robust, one-step electrochemical technique to generate surface-bound conjugated polymers. The electrochemical reduction of arene diazonium salts at the surface of a gold electrode is used to generate tethered bromobenzene monolayers quickly. The oxidative addition of reactive Ni(0) across the aryl halide bond is(More)
Surface-initiated ring-opening polymerization (SI-ROP) of polycaprolactone (PCL) and polylactide (PLA) polymer brushes with controlled degradation rates were prepared on oxide substrates. PCL brushes were polymerized from hydroxyl-terminated monolayers utilizing triazabicyclodecene (TBD) as the polymerization catalyst. A consistent brush thickness of 40 nm(More)
While ring-walking is a critical step in transition metal catalyzed cross-coupling reactions, the associated metastable intermediates are often difficult to isolate and characterize. In this work, theoretical structures and energetics for ring-walking and oxidative addition of zerovalent nickel with 1-bromo-2-methylbenzene, 2-bromopyridine,(More)
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