Ordered binary crystals viacocrystallisation of quasiracemic Pd(ii) complexes in a borderline regime between inertness and lability

Abstract

Square planar complexes of the type [2-(1-aminoethyl)phenyl-κ²C¹,N]chloro(py-κN)palladium(II) (py = pyridine derivative) have been prepared by cyclopalladation of 1-phenylethylamine. When opposite enantiomers of the chiral amine and different pyridine ligands were coordinated to the metal, quasiracemic complexes were obtained. The racemisation speed of solutions containing equimolar amounts of such quasiracemic complexes was used to test the compounds for inertness: slow ligand exchange was found for methylated pyridines. Enantiomerically pure complexes of opposite chirality with the electron rich ligands 2,6-collidine and 2,4,6-lutidine were successfully cocrystallised: They form a well-ordered binary solid in which four independent molecules, two of each constituent, are related by pseudo symmetry operations. This quasiracemate as well as its components and the true racemates of the latter were characterised by single crystal X-ray diffraction. The heterochiral crystals, both the cocrystal as well as the racemates, show better space filling than the homochiral solids.