The Study of Rhodium and Silver Complexes with Thioether- and Sulfoxide-Functionalized N-Heterocyclic Carbene Ligands
Date Issued
2014
Date
2014
Author(s)
Yu, Chi-Ying
Abstract
We have synthesized a series of thioether- and sulfoxide-functionalized NHCs (S-NHC and SO-NHC) ligands and investigated their complexes of rhodium(I) and silver(I). All synthesized complexes [(S-NHC)Rh(COD)]X, [(SO-NHC)Rh(COD)]X (X = Cl or BF4), (S-NHC)-AgCl and [(SO-NHC)2Ag]+AgCl2- have been fully characterized by detailed NMR studies and molecular structures of some of these
complexes were elucidated by X-ray crystallography.
In rhodium complexes, competing coordination with metal center between sulfur atom and chloride ion was found in neutral complexes with S- and SO-NHC. The exchange of S- and O-bound coordination in the cationic complexes of SO-NHC-rhodium is proposed. Experimental and computing results are consistently support that the two modes of coordination are subject to the exchanging process with the O-bound species being thermodynamically more favored. Both S- and SO-NHC silver(I) complexes showed good activity in intramolecular cyclization of acetylenic acids, giving five-membered ring products in excellent to good yield as well as good selectivity.
Subjects
硫醚
亞碸-氮雜環碳烯
Type
thesis
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