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.