Template-controlled assembly of ditopic catechol phosphines: a strategy for the generation of complexes of bidentate phosphines with different bite angles.

A rational approach to the synthesis of heterobi- or -trimetallic complexes based upon self-assembly of a flexible ditopic catechol-phosphine ligand with [(cod)PdCl(2)] and simple metal halides such as GaCl(3), BiCl(3), SnCl(4), or ZrCl(4) is described. All products were characterized by spectroscopic and analytical data and single-crystal X-ray diffraction studies. The molecular structures can be described in terms of cis-configured palladium complexes with supramolecular bisphosphine ligands that are formed by the assembly of two phosphine catecholate fragments on a main group/transition metal template. Of particular interest are the distinct decreases in P-Pd-P bite angles and P...P dist…