Chemistry Commons^™

Synthesis Of Ni(Ii) Complexes For Allylic C(Sp3)-H Bond Activation For Aerobic Oxidation Catalysis, Shagana Kukendran

Electronic Thesis and Dissertation Repository

Nickel is a widely abundant and inexpensive metal. Catalysts are substances that remain unconsumed and increase the rate of reactions by reducing the activation energy barrier, often by providing an alternative route. The main goal of this study is to prepare Ni(II) complexes that can promote a catalytic aerobic oxidation reaction by breaking allylic C-H bonds. Based on previous studies, allylnickel N-heterocyclic carbene complexes react with molecular oxygen to give useful carbonyl compounds with a Ni(II)-OH by-product, which undergoes dimerization. In order to achieve catalysis, dimerization of the Ni(II)-OH should be prevented and C-H activation has to be achieved to …

Coinage Metal Silylphosphido Complexes Stabilized By N-Heterocyclic Carbene Ligands, Bahareh Khalili Najafabadi

Electronic Thesis and Dissertation Repository

N-Heterocyclic carbenes (NHCs) are strong σ-donating ligands and thus, promising candidates for decorating and stabilizing metal-phosphide nanoclusters. While much research has been focused on the coordination of NHC ligands to different coinage metal centers in order to synthesize mononuclear organometallic complexes, their application in nanocluster chemistry has been relatively unexplored. The work described in this thesis involves employment of NHC ligands for stabilizing coinage metal t-butylthiolate and silylphosphido complexes. These complexes are promising molecular precursors for formation of larger NHC-stabilized nanoclusters.

In particular, the ligation of NHCs to [CuS^tBu] and [AgS^tBu] was developed as an …

Novel Thiophene Supported N,N'-Chelating Ligands And Their Main Group Compounds, Jacquelyn T. Price

Electronic Thesis and Dissertation Repository

Main group chemistry has advanced from studying fundamental curiosities, including low oxidation state, low-valent, p-block elements to tailoring these unique, reactive species for specific functional applications. This thesis examines the structure, bonding and reactivity of select group 13, 14 and 15 elements supported by N,N'-chelating ligands decorated with either thiophene, benzo[1,2-b:5,6-b']dithiophene or bis(2,5-dimethylthienyl)ethene substituents and allowing for subsequent reactivity and photophysical properties to be determined.

The synthesis of a new diamino ligand containing a thiophene ring in the backbone was used to support a 7-membered phosphenium cation. The 1:1 stoichiometric reaction between the amine:chlorophosphine was dependant on the substitution …