GROUP 10 TRANSITION METAL CHEMISTRY OF SULFUR-FUNCTIONALIZED/NON-CLASSICAL N-HETEROCYCLIC CARBENE LIGANDS

Abstract

This thesis reports studies on sulfur-functionalized N-heterocyclic carbene (NHC) complexes, and the determination of donor strengths of non-classical NHCs. In the first part, a variety of Pd(II), Ni(II) and Pt(II) complexes bearing CSC-pincer type, sulfoxide, thiolato or sulfonate functionalized NHC ligands have been synthesized. The catalytic activities of selected complexes were investigated in C-C coupling or hydroamination reactions. In the second part, a series of hetero-bis(carbene) complexes trans-[PdBr₂(<i>ⁱ</i>Pr₂-bimy)L] (<i>ⁱ</i>Pr₂-bimy = 1,3-diisopropylbenzimidazolin-2-ylidene; L = non-classical carbene) have been synthesized. The donating abilities of the transoid ligands L, which include a perimidine derived NHC, saturated 6- and 7-membered NHCs and 1,2,3-triazolin-5-ylidenes in this study, were determined by analyses of ¹³C NMR spectra of those complexes. Catalytic activities of complexes bearing 1,2,3-triazolin-5-ylidenes and their trifluoroacetato analogues were examined in the direct arylation of pentafluorobenzene.