Novel synthetic routes to several new, differentially substituted ruthenium tris(4,4 disubstituted-2,2-bipyridine)...

The stepwise synthesis of several novel Ru(tris(pp)) complexes (pp = 4,4'-disubstituted-2,2'-bipyridine; substituent = H, Me, chiral ester, or chiral amide) is described, where the pp ligands may be the same, or different, in each complex. All of the complexes detailed have been resolved into their pure delta- and lambda-enantiomers or diastereomers. The complexes, which are prepared starting from RuCl3, contain novel ligand architectures, with a range of chiral esters and amides attached to the 4,4'-positions of the bpy ligands. It was postulated that these chiral groups would be capable of inducing chirality at the metal center, but our investigations have shown this not to be the case, and in all reactions completely racemic products were formed. Resolution by chiral HPLC, and the subsequent characterization of the products through NMR, UV-vis, and circular dichroism (CD) spectroscopy, has been carried out; the characteristics of the CD spectra have been discussed with respect to the electron-donating/ withdrawing ability of the groups at the 4,4'-positions. The X-ray crystal structure of the optically pure complex lambda-[Ru(dmbpy)2(4,4'-bis((R)-(+)-alpha-phenylethylamido)-2,2'-bipyridine)] x 2PF6 x 2CHCl3 was obtained and solved using direct methods. This result, in conjunction with the CD spectra, enabled the complete and unambiguous assignment of the stereocenters of all of the novel Ru(tris(bpy)) complexes prepared in this investigation.