N-Heterocyclic carbene metal complexes : synthesis, kinetics, reactivity, and recycling with polymers /

Bibliographic Details
Main Author: Su, Haw-Lih
Other Authors: Bergbreiter, David E. (Thesis advisor)
Format: Thesis eBook
Language:English
Published: [College Station, Tex.] : [Texas A&M University], [2012]
Subjects:
Online Access:Link to OAK Trust copy

MARC

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245 1 0 |a N-Heterocyclic carbene metal complexes :  |b synthesis, kinetics, reactivity, and recycling with polymers /  |c by Haw-Lih Su. 
264 1 |a [College Station, Tex.] :  |b [Texas A&M University],  |c [2012] 
300 |a 1 online resource. 
336 |a text  |b txt  |2 rdacontent 
337 |a computer  |b c  |2 rdamedia 
338 |a online resource  |b cr  |2 rdacarrier 
500 |a "Major Subject: Chemistry" 
588 |a Description from author supplied metadata (automated record created 2012-10-22 13:24:58). 
502 |b Doctor of Philosophy  |c Texas A&M University  |d 2011  |o http://hdl.handle.net/1969.1/ETD-TAMU-2011-08-10082 
504 |a Includes bibliographical references. 
516 |a Text (Dissertation) 
520 3 |a N-Heterocyclic carbenes (NHCs) are good ligands to most transition metals forming stable complexes. Many of the NHC-metal complexes are now widely used catalysts. However, the usage of these catalysts encounters the general problems associated with homogeneous catalysis: the purification of the catalysis reaction products is often time-consuming and generates large amounts of waste. Moreover, the toxic or expensive catalysts are difficult to be separated, recycled, and reused. Chapters II and III of this dissertation focus on addressing these problems through the development of an easier and "greener" process to improve the usage of some NHC-metal complexes. Polymer-supported catalysts and polymer-supported sequestrants were prepared and used to facilitate the separation/recycling of catalysts and the purification of products. These polymer-supported ligands, catalysts, and sequestrants showed comparable reactivity to their low molecular weight counterparts and had different solubility properties due to the nature of polymers. Using these materials with the corresponding operations provides simple methods to separate deeply colored, metal-containing by-products from the reaction mixtures. Chapter IV of this dissertation aims at solving a fundamental question about the nature of NHC-silver(I) complexes. The NHC-silver(I) complex is an important synthetic intermediate as it can be used to prepare other NHC-metal complexes through transmetallation. The carbene carbon of an NHC-silver(I) complex in ¹³C NMR spectra was usually reported as a doublet of doublets or as a singlet in different cases. This phenomenon was explained with a ligand exchange mechanism proposed twelve years ago. However, few reports are available in the literature about the mechanism of the NHC ligand exchange processes at silver. In order to facilitate the study of the solution behaviors of NHC-silver(I) complexes, ¹³C-labeled NHC-silver(I) complexes were prepared and studied using variable temperature ¹³C NMR spectroscopy. This study could be useful for future applications of ligand transferring from silver to other metals for the preparation of NHC-metal complexes. 
500 |a Electronic resource. 
650 4 |a Major Chemistry. 
653 |a dynamic 
653 |a NHC 
653 |a NHC-metal complexes 
653 |a catalyst recycling 
653 |a N-Heterocyclic carbene 
653 |a polymer-support 
653 |a VT NMR 
700 1 |a Bergbreiter, David E.,  |e thesis advisor. 
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