Rigid bis-zinc(II) salphen building blocks for the formation of template-assisted bidentate ligands and their application in catalysis.

The template-induced formation of chelating bidentate ligands by the selective self-assembly of two monodentate pyridyl phosphorus ligands on a rigid bis-zinc(II) salphen template with two identical binding sites was studied. Using UV-vis, NMR-spectroscopy and X-ray analysis the formed structures were unambiguously proven. The application of these templated bidentate ligands in transition metal catalysis showed, in most cases, typical bidentate character. Compared to previous work based on a more flexible bis-zinc(II) porphyrin template, the current catalytic data suggest that the rigidity of the template is not an important factor for the improvement of the regio- and enantioselectivity under the applied reaction conditions.