A wide range of functionalized pyridine ligands have been employed to synthesize a variety of Pd(II) complexes of the general formulas [PdL4](NO3)2 and [PdL2Y2], where L = 4-X-py and Y… Click to show full abstract
A wide range of functionalized pyridine ligands have been employed to synthesize a variety of Pd(II) complexes of the general formulas [PdL4](NO3)2 and [PdL2Y2], where L = 4-X-py and Y = Cl– or NO3–. Their structures have been unambiguously established via analytical and spectroscopic methods in solution (NMR spectroscopy and mass spectrometry) as well as in the solid state (X-ray diffraction). This in-depth characterization has shown that the functionalization of ligand molecules with groups of either electron-withdrawing or -donating nature (EWG and EDG) results in significant changes in the physicochemical properties of the desired coordination compounds. Downfield shifts of signals in the 1H NMR spectra were observed upon coordination within and across the complex families, clearly indicating the relationship between NMR chemical shifts and the ligand basicity as estimated from pKa values. A detailed crystallographic study has revealed the operation of a variety of weak interactions, which may be factors explaining aspects of the solution chemistry of the complexes. The Pd(II) complexes have been found to be efficient and versatile precatalysts in Suzuki–Miyaura and Heck cross-coupling reactions within a scope of structurally distinct substrates, and factors have been identified that have contributed to efficiency improvement in both processes.
               
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