Synthesis and characterization of para-pyridinyl PCP pincer complexes

Abstract

This thesis is divided into two chapters.

In chapter 1, a general introduction to pincer complexes will be given, which includes some early findings, metallation methods, pincer complex modifications and their application in catalysis. In addition, the synthetic methodologies to chiral PCP (phosphorus-carbon-phosphorus) pincer ligands were highlighted.

In chapter 2, the synthesis and characterization of the PCP pincer ligand 3,3'-(pyridine-3,5-diyl)bis(3-(diphenylphosphino)-1-phenylpropan-1-one) and its platinum and palladium complexes were documented. The synthesis of the PCP ligand via asymmetric hydrophosphination gave excellent yields, with dr up to 97:3 and >99% ee. The platinum and palladium pincer complexes were synthesized in moderate yields through metallation of the crude ligand with PtCl2(NCMe)2 and PdCl2(NCMe)2 respectively. Furthermore, the N-methylated Pd(PCP) complex was synthesized from the reaction between Pd(PCP) complex and iodomethane. The metal-carbon bond lengths of the N-substituted PCP pincer complexes were found to be the shortest, which could possibly display the highest catalytic reactivity in nucleophilic reactions.