Advisor

Mead, Keith T.

Committee Member

Sygula, Andrzej

Committee Member

Wipf, David O.

Committee Member

Emerson, Joseph P.

Committee Member

Mlsna, Todd E.

Date of Degree

1-1-2016

Document Type

Dissertation - Open Access

Abstract

The first stable “free” N-heterocyclic carbene (NHC) was isolated in 1991, since then many classes of NHCs were synthesized and isolated. N-heterocyclic carbene ligands have become a common ligand in the synthesis of metal complexes, due to their strong σ-donation with poor πeptor ability. Among all the NHC metal complexes, Hollis group was interested in exploring -NHC pincer complexes. In 2005, Hollis and co-workers synthesized and isolated first achiral -NHC zirconium pincer amido complex and studied its catalytic ability to perform intramolecular hydroamination of aminoalkenes. Later, Hollis group designed and developed new NHCs with a saturated chiral backbone, and used these new ligands to generate a new series of metal complexes. This dissertation is focused on the design, synthesis and characterization of several chiral bi-dentate NHC ligands with varying substituents on the backbone. These NHC ligands were used to synthesize several chiral mono, bis and tris amido -NHC zirconium pincer complexes. Further, transmetallation to cobalt complexes were achieved. Intramolecular hydroamination was measured for several chiral bis and tris amido -NHC pincer zirconium catalysts. Variants of these catalytic systems were generated with differing steric hinderance and electronic structure. The enantioselectivity of these novel new molecules were studied.

URI

https://hdl.handle.net/11668/19877

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