| Title: |
The development of next generation, unsymmetrical CCC-NHC pincer ligand architectures and metalation to form unsymmetrical CCCNHC pincer Ta complexes |
| Authors: |
Box, Hannah Killian |
| Contributors: |
Keith T. Mead; Andrzej Sygula; Joseph P. Emerson; Todd E. Mlsna; Debbie J. Beard |
| Source: |
http://sun.library.msstate.edu/ETD-db/theses/available/etd-04282015-140641/. |
| Publisher Information: |
MSSTATE |
| Publication Year: |
2015 |
| Collection: |
Mississippi State University: ETD Collection |
| Subject Terms: |
Chemistry |
| Description: |
The impact of N -heterocyclic carbenes (NHC) as ligands for transition metal catalysis has been rigorously investigated since their isolation by Arduengo in 1991. NHCs have become abundant in late-transition metal chemistry. This is attributed to NHCs being stronger sigma-donors than even the strongest phosphine analogues, thus constructing a transition metal-NHC complex with improved stability, catalytic reactivity, and selectivity. Additionally, pincer ligands have become recognized as an important class of ligands for transition metal complexes. The unique steric and electronic tunability of pincer ligands has resulted in pincer-transition metal complexes being exploited as catalysts for a multitude of transformations. Both ligand classes, NHC and pincer, have been reported as stable organometallic catalysts that demonstrate high catalytic activity. The combination of these two ligand systems by incorporation of NHCs into pincer ligands has attracted considerable attention. NHC pincer systems have been reported as stable organometallic catalysts that demonstrate high catalytic activity. The expansion of CCC-NHC ligand precursor methodologies and application of the newly reported methodologies in order to diversify CCC-NHC ligand architectures is reported. Extension of the amine elimination methodology yielded unsymmetrical CCCNHC Ta pincer complexes. Studies on the manipulation of the previously reported symmetrical CCC-NHC pincer Ta complexs coordination sphere to synthesize a rare Ta diimido complex with unique reactivity towards advantageous proton sources and oxidative amination of aminoalkenes are also expanded upon. These next generation catalysts developed from these architectures may prove useful in catalyzing a broad array of transformations not previously accessible through the four standard NHC containing pincer ligand architectures. |
| Document Type: |
text |
| File Description: |
application/pdf |
| Language: |
English |
| Availability: |
http://sun.library.msstate.edu/ETD-db/theses/available/etd-04282015-140641/ |
| Rights: |
unrestricted ; I hereby certify that, if appropriate, I have obtained and attached hereto a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, Dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted is the same as that approved by my advisory committee. I hereby grant to Mississippi State University Libraries or its agents the non-exclusive license to archive and make accessible, under the conditions specified below, my thesis, Dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, Dissertation or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, Dissertation, or project report. |
| Accession Number: |
edsbas.2BC160F8 |
| Database: |
BASE |