BIPYRIDYL-METAL COMPLEXES .2. SYNTHESIS AND CHARACTERIZATION OF PALLADIUM(II) CHLORIDE COMPLEXES OF 6-FERROCENYL-2,2'-BIPYRIDINE, 2-FERROCENYL-1, 10-PHENANTHROLINE, AND 6-RUTHENOCENYL-2,2'-BIPYRIDINE AND THE SINGLE-CRYSTAL X-RAY STRUCTURE OF (1,1'-BIS(2,2'-BIPYRID-6-YL)FERROCENE-N,N')PALLADIUM CHLORIDE

The coordination chemistry of a series of ferrocenyl- and ruthenocenylbipyridines such as 6-ferrocenyl-2,2'-bipyridine (HL1), 1,1'-bis(2,2'-bipyrid-6-yl)ferrocene (HL2), 2-ferrocenyl-1,10-phenanthroline (HL3), and 2-(2,2'-bipyrid-6-yl)-1-((dimethylamino)methyl)ferrocene (HL5) has been studied. The reaction of dichloro(eta(4)-1,5-cyclooctadienyl)palladium with a series of ferrocenylbipyridine and ferrocenyl-phenanthroline ligands gives the new complexes [(L1)PdCl], [(L2)PdCl] (L is the anion of HL in which a cyclopentadienyl proton alpha to the bipyridyl sustituent has been removed; e.g., L1 refers to HL1 with one cyclopentadienyl proton alpha to the bipyridyl removed and the position palladated), and [(HL3)PdCl2]. The synthesis of the new ligand 2-(2,2'-bipyrid-6-yl)-1-((dimethylamino)methyl)ferrocene (HL5) from the direct reaction of 2-lithio-1-((dimethylamino)methyl)ferrocene with 2,2'-bipyridine is described, in addition to the characterization of 6-ruthenocenyl-2,2'-bipyridine and 2-ruthenocenyl-1,10-phenanthroline. The single-crystal X-ray structure of the violet complex [(L2)PdCl.0.5CH2Cl2] was determined and gave the following structural data: orthorhombic, Pbca, a = 13.879 (3) angstrom, b = 19.329 (3) angstrom, c = 20.854 (4) angstrom, V = 5594.4 (18) angstrom 3, C30H21ClFeN4Pd.0.5CH2Cl2, Z = 8, rho(calc) = 1.612 g cm-3, mu = 1.37 mm-1, R(F) = 0.076, R(wF) = 0.093, GOF = 1.02. Complexes [(L)PdCl] (L = L1, L2) are the first reported examples of a tridentate coordination mode of a bipyridyl ligand containing ferrocene.