Executive Summary : | The study focuses on the development of new ancillary ligands with variable donors and linkers, easy accessibility, and effective steric and stereogenic control. Imidazolylidene-based N-heterocyclic carbenes (NHCs) are widely used in synthetic applications, while donor-functionalized NHCs with chelating ligand frameworks are more versatile. Similarly, pyrrolin-2-ylidene-based cyclic(alkyl)(amino)carbenes (CAACs) have seen a significant rise in recent years, outperforming NHCs on many occasions. However, CAACs lack additional donor functionalization. The researchers have recently obtained access to a picolyl tethered CAAC system (picoCAAC; N,C bidenate) and isolated its CuCl complex. The project aims to expand this chemistry by scanning transition metals and preparing a pool of complexes for further reactivity. Synthetically useful catalytic processes will be targeted, including hydroelementation of polar and non-polar unsaturated organics, C-C cross-coupling, and olefin metathesis. The reaction mechanism will be investigated in detail. Other variants of picoCAAC will be considered by changing the linker length and type. Other donor motifs such as quinolinyl, benzoxazolyl, benzthiazolyl, and bipyridinyl will also be tested. Additionally, donor-functionalized cyclic(amino)(barrelene)carbenes (CABCs) will be investigated on the side. |