Diastereoselective Synthesis, Spectroscopy, and Electrochemistry of Ruthenium(II) Complexes of Substituted Pyrazolylpyridine Ligands.

Abstract

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-tetrahydroindazoles with substituents R = H, CH(3), Ph, or C(6)H(4)-4"-COOX where X = H, CH(3), or C(2)H(5)). These were fully characterized by (1)H- and (13)C-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).H(2)O 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 (1)H-NMR and confirmed by X-ray crystallography for one such stereomer (beta-[Ru(bpy)(5)(2)](PF(6))(2), R = C(6)H(4)-4"-COOC(2)H(5)). 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)](PF(6))(2) (C(52)H(50)N(8)O(4)F(12)P(2)Ru) with Mo Kalpha (lambda = 0.710 73 Å) radiation at 295 K: a = 28.442(13) Å, b = 18.469(15) Å, c = 23.785(9) Å, 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 > 4sigma(F ).