Pairing of propellers: dimerization of octahedral ruthenium(II) and osmium(II) complexes of eilatin via pi-pi stacking featuring heterochiral recognition.
Five octahedral eilatin complexes of the type [M(L-L)(2)(eilatin)](2+) (M = Ru, Os; L-L = bipyridyl-type ligands) were synthesized, and their dimerization via pi-pi stacking was studied by crystallography and (1)H NMR techniques. The X-ray structures of these racemic complexes were solved and revealed that the eilatin complexes are organized as discrete dimers in which the eilatin residues of each complex are stacked in centrosymmetric packing. Chemical shift dependence on concentration in the (1)H NMR spectra support fast dimer-monomer equilibrium, and the structures of the dimers in acetonitrile solution are proposed to be analogous to their solid-state structures. Dimerization constants in acetonitrile were measured for the five racemic eilatin complexes that exhibit different structural parameters, as well as for the two enantiomeric forms of one of these complexes. They were found to be independent of the metal (Ru vs Os), strongly dependent on the steric effects introduced by the L-L ligands (2,2'-bipyridine, 1,10-phenanthroline, 2,9-dimethyl-1,10-phenanthroline, and 2,2'-biquinoline), and dependent on the optical purity of the complexes. A clear preference for heterochiral over homochiral dimer formation was demonstrated. This is the first report of chiral recognition in solution, exhibited by simple chemical systems held solely by pi-stacking interactions.