Inorganic Chemistry, Vol.35, No.19, 5445-5452, 1996
Diastereoselective Synthesis, Spectroscopy, and Electrochemistry of Ruthenium(II) Complexes of Substituted Pyrazolylpyridine Ligands
We report the synthesis of the hetero- and homoleptic ruthenium(II) complexes Ru(bpy)(2)L(2+), Ru(bpy)L(2)(2+) (bpy is 2,2’-bipyridine), and RuL(3)(2+) of six new bidentates L, the substituted pyrazolylpyridines 1-6 (1-substituted-3-(2-pyridinyl)-4,5,6,7-tetrahydroindazooles with substituents R = H, CH3, Ph, or C6H4-4(")-COOX where X = H, CH3, or C2H5). These were fully characterized by H-1- and C-13-NMR spectroscopy and elemental analysis. The UV-visible spectra and redox properties of the complexes, some in the ruthenium(III) and reduced bipyridine oxidation states, are also discussed. The substituents R played a role in determining the stereochemistry of the Ru(bpy)L(2)(2+) and RuL(3)(2+) products. The reaction of Ru(DMSO)(4)Cl-2 with 3 equiv of L bearing aromatic substituents gave only meridional RuL(3)(2+) isomers. The one-step reaction of Ru(bpy)Cl-3 . H2O with 2 equiv of L provided a mixture of the three possible Ru(bpy)L(2)(2+) isomers, from which one symmetric isomer (labeled beta) was isolated pure. A trans arrangement of the pyrazole groups was deduced by H-1-NMR and confirmed by X-ray crystallography for one such stereomer (beta-[Ru(bpy)(5)(2)](PF6)(2), R = C6H4-4(")-COOC2H5). In contrast, Ru(DMSO)(4)Cl-2 reacted with 2 equiv of L and then 1 equiv of bpy to selectively form the other symmetric isomer (labeled alpha) where the pyridine groups of L are trans. Crystal data for beta-[Ru(bpy)(5)(2)](PF6)(2) (C52H50N8O4F12P2Ru) With MO K alpha (lambda = 0.710 73 Angstrom) radiation at 295 K : a = 28.442(13) Angstrom, b = 18.469(15) Angstrom, c = 23.785(9) Angstrom, beta = 116.76(0)degrees, monoclinic, space group C2/c, Z = 8. Fully anisotropic (except for H and disordered F atoms), full-matrix, weighted least-squares refinement on F-2 gave a weighted R on F-2 of 0.2573 corresponding to R on F of 0.1031 for data where F > 4 sigma(F).
Keywords:CHELATION-CONTROLLED REGIOSELECTIVITY;EXCITED-STATES;POLYPYRIDINE COMPLEXES;REDUCTION PRODUCTS;ELECTRON-TRANSFER;2;2’-BIPYRIDINE COMPLEXES;HETEROCYCLIC LIGANDS;BIPYRIDINE COMPLEXES;CRYSTAL-STRUCTURE;REDOX POTENTIALS