Synthesis, Structure, Spectroscopic Properties, and Electrochemical Oxidation of Ruthenium(II) Complexes Incorporating Monocarboxylate Bipyridine Ligands

[Ru(bpy)₂(Mebpy-COOH)](PF₆)₂·3H₂O (1), [Ru(phen)₂(Mebpy-COOH)](ClO₄)₂·5H₂O (2), [Ru(dppz)₂(Mebpy-COOH)]Cl₂·9H₂O (3), and [Ru(bpy)(dppz)(Mebpy-COOH)](PF₆)₂·5H₂O (4) (bpy = 2,2‘-bipyridine, Mebpy-COOH = 4‘-methyl-2,2‘-bipyridine-4-carboxylic acid, phen = 1,10-phenanthroline, dppz = dipyrido[3,2,-a;2‘,3-c]phenazine) have been synthesized and characterized spectroscopically and by microanalysis. The [Ru(Mebpy-COOH)(CO)₂Cl₂]·H₂O intermediate was prepared by reaction of the monocarboxylic acid ligand, Mebpy-COOH, with [Ru(CO)₂Cl₂]_n, and the product was then reacted with either bpy, phen, or dppz in the presence of an excess of trimethylamine-N-oxide (Me₃NO), as the decarbonylation agent, to generate 1, 2, and 3, respectively. For compound 4, [Ru(bpy)(CO)Cl₂]₂ was reacted with Mebpy-COOH to yield [Ru(bpy)(Mebpy-COOH)(CO)Cl](PF₆)·H₂O as a mixture of two main geometric isomers. Chemical decarbonylation in the presence of dppz gave 4 also as a mixture of two isomers. Electrochemical and spectrophotometric studies indicated that complexes 1 and 2 were present as a mixture of protonated and deprotonated forms in acetonitrile solution because of water of solvation in the isolated solid products. The X-ray crystal structure determination on crystals of [Ru(bpy)₂(MebpyCOO)][Ru(bpy)₂(MebpyCOOH)]₃(PF₆)₇, 1a, and [Ru(phen)₂(MebpyCOO)](ClO₄)·6H₂O, 2a, obtained from solutions of 1 and 2, respectively, revealed that 1a consisted of a mixture of protonated and deprotonated forms of the complex in a 1:3 ratio and that 2a consisted of the deprotonated derivative of 2. A distorted octahedral geometry for the Ru^II centers was found for both complexes. Upon excitation at 450 nm, MeCN solutions of the protonated complexes 1−4 were found to exhibit emission bands in the 635-655 nm range, whereas the corresponding emission maxima of their deprotonated forms were observed at lower wavelengths. Protonation/deprotonation effects were also observed in the luminescence and electrochemical behavior of complexes 1−4. Comprehensive electrochemical studies in acetonitrile show that the ruthenium centers on 1, 2, 3, and 4 are oxidized from Ru^II to Ru^III with reversible potentials at 917, 929, 1052, and 1005 mV vs Fc^0/+ (Fc = ferrocene), respectively. Complexes 1 and 2 also exhibit an irreversible oxidation process in acetonitrile, and all compounds undergo ligand-based reduction processes.