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Date of Award

Summer 8-15-2017

Author's School

Graduate School of Arts and Sciences

Author's Department


Degree Name

Doctor of Philosophy (PhD)

Degree Type



The importance of Pd-catalyzed C—H functionalization reactions for chemical transformations has been widely studied over the last several decades. Much of the research to date has focused on conventional Pd0/II catalytic cycles. However, more recent studies have shown that many transformations can also follow a PdII/IV catalytic cycle. High-valent PdIII and PdIV species are often proposed to be important intermediates in such transformations. C—H coupling reactions involving high-valent intermediates often involve the oxidation of a PdII species to a PdIII or PdIV complex, which can then undergo subsequent C—heteroatom bond formation. However, the need for harsh oxidants and reaction conditions in many of these reactions hinders their practical applicability. The focus of this work is to study the properties and reactivity of PdII, PdIII, and PdIV complexes through modifications of the supporting macrocyclic ligands. Another goal of this work is to probe the ability of these complexes to facilitate C—H activation and C—heteroatom bond formation reactions using environmentally benign oxidants.

Our lab reported the synthesis and characterization of the first organometallic mononuclear PdIII complexes stabilized by the tetradentate ligand N,N’-di-tert-butyl-2,11-diaza[3,3](2,6)pyridinophane (tBuN4). In order to further probe the Pd chemistry with this class of ligands, we prepared ligands with modifications to the steric bulk on the amine groups. In the first study detailed in chapter 2, the synthesis and characterization of PdII and PdIII complexes supported by N,N’-di-neo-pentyl-2,11-diaza[3,3](2,6)-pyridinophane(NpN4) and N,N’-di-benzyl-2,11-diaza[3,3](2,6)-pyridinophane(BzN4) is reported. Interestingly, the spectroscopic and crystallographic property of the newly synthesized complexes falls between the tBuN4 and MeN4 complexes. The C—C and C—heteroatom bond formation reactivity of the NpN4 and BzN4 supported complexes is also similar to our group’s previously reported complexes.

We also prepared and studied a series of Pd complexes bearing a modified tetradentate pyridinophane ligand, tBuN3CH. Essentially, we have replaced one of the nitrogen donor atoms from the N4 ligand with a carbon atom and have also introduced a new C—H bond. Due to its expected positioning near the metal center, this bond has the potential to undergo intramolecular C—H bond activation. In order to study the reactivity of this ligand, electronic modifications were made by substituting various electron-donating and withdrawing groups in the para position to this new C—H bond. In chapter 3, the synthesis and characterization of a series of PdII, PdIII, and PdIV complexes stabilized by the N3CH ligand is reported. Interestingly, a spectroscopic and crystallographic study of the pRN3CHPdII(OAc)2 complexes reveals that the Cipso—H bond remains unactivated at the PdII stage. However, upon oxidation to PdIII, the Cipso—H bond is activated.

Interestingly, we discovered that the aerobic oxidation of the PdII complex [pRN3CHPdII(MeCN)](BF4) leads to the formation of the PdIII complex [pRN3CHPdIII(MeCN)](ClO4)2 at room temperature. Surprisingly, the C—H activation reaction proceeds in the presence of oxygen without the need for external base. Furthermore, the moderate rate of the reaction allowed us to investigate the mechanism of the reaction by utilizing kinetics and UV-Vis spectroscopy. Detailed mechanistic studies revealed that C—H activation of the Cipso—H bond is the rate determining step of the reaction.


English (en)

Chair and Committee

Liviu M. Mirica

Committee Members

John R. Bleeke, William E. Buhro, Nigam P. Rath, Bryce Sadtler,


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