Palladium(II) Complexes of Readily Functionalized Bidentate 2-Pyridyl-1,2,3-triazole “Click” Ligands: A Synthetic, Structural, Spectroscopic, and Computational Study

Abstract

The Cu(I)-catalyzed 1,3-cycloaddition of organic azides with terminal alkynes, the CuAAC “click” reaction is currently receiving considerable attention as a mild, modular method for the generation of functionalized ligand scaffolds. Herein we show that mild one-pot “click” methods can be used to readily and rapidly synthesize a family of functionalized bidentate 2-pyridyl-1,2,3-triazole ligands, containing electrochemically, photochemically, and biologically active functional groups in good to excellent yields (47–94%). The new ligands have been fully characterized by elemental analysis, HR-ESI-MS, IR, ¹H and ¹³C NMR and in three cases by X-ray crystallography. Furthermore we have demonstrated that this family of functionalized “click” ligands readily form bis-bidentate Pd(II) complexes. Solution studies, X-ray crystallography, and density functional theory (DFT) calculations indicate that the Pd(II) complexes formed with the 2-(1-R-1H-1,2,3-triazol-4-yl)pyridine series of ligands are more stable than those formed with the [4-R-1H-1,2,3-triazol-1-yl)methyl]pyridine “click” ligands.