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 …

Design, Synthesis, And Oxidation Reactivity Of Palladacyclic Complexes Containing N-Donor Ligands, Ava Behnia

Electronic Thesis and Dissertation Repository

This thesis describes the synthesis and reactivity of complexes containing the cycloneophyl-Pd(II) group, PdCH₂CMe₂C₆H₄, in combination with N-donor ligands. These compounds contain both alkyl- and arylpalladium bonds and the selectivity of bond cleavage in reactions with oxidants and protic reagents is studied, often involving oxidative addition and reductive elimination reaction sequences.

The diimine ligand in [Pd(CH₂CMe₂C₆H₄)(MesN=CH-CH=NMes)] does not support formation of stable palladium(IV) complexes, but reactions with Br₂ or I₂ lead to reductive elimination by C-C bond formation of 1,1-dimethylcyclobutabenzene while …