Electronic Theses and Dissertations

Date of Award

1-1-2013

Document Type

Dissertation

Degree Name

Ph.D. in Chemistry

Department

Chemistry and Biochemistry

First Advisor

Thedford K Hollis

Second Advisor

Daniel Mattern

Third Advisor

Mitchell A. Avery

Relational Format

dissertation/thesis

Abstract

The previously reported amine elimination methodology for the metalation of CCC-NHC pincer ligand precursors has been extended to other early-transition metals and ligands. Specifically, synthetic results for the preparation of imidazole based CCC-NHC pincer Ti (IV), CCC-NHC pincer Ta (V) will be discussed. In addition, the synthesis of a new triazole based CCC-NHC pincer ligand precursor and its metalation with Ta (V) will be presented. Coordination sphere manipulation of the new pincer complexes using TMSCl for the Ti complex and lithium t-butylamide for the Ta complexes is also discussed. The reaction of the initial Ta CCC-NHC complex with lithium t-butylamide is of particular interest as it is the first X-ray crystallographically determined molecular structure of an early-transtion metal anionic N-heterocyclic carbine complex. Catalytic results in hydroamination/cyclization with the Ti complexes and oxidative amination using the Ta complexes will also be reported.

Included in

Chemistry Commons

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