cis-Bis(bipyridine)ruthenium Imidazole Derivatives: A Spectroscopic, Kinetic, and Structural Study.
The ruthenium bis(bipyridine) complexes cis-[Ru(bpy)(2)Im(OH(2))](2+), cis-[Ru(bpy)(2)(Im)(2)](2+), cis-[Ru(bpy)(2)(N-Im)(2)](2+), cis-[Ru(dmbpy)(2)Im(OH(2))](2+), cis-[Ru(dmbpy)(2)(N-Im)(OH(2))](2+)(bpy = 2,2'-bipyridine, dmbpy = 4,4'-dimethyl-2,2'-bipyridine, Im = imidazole, N-Im = N-methylimidazole), have been synthesized under ambient conditions in aqueous solution (pH 7). Their electrochemical and spectroscopic properties, absorption, emission, and lifetimes were determined and compared. The substitution kinetics of the cis-[Ru(bpy)(2)Im(OH(2))](2+) complexes show slower rates and have lower affinities for imidazole ligands than the corresponding cis-[Ru(NH(3))(4)Im(OH(2))](2+) complexes. The crystal structures of the monoclinic cis-[Ru(bpy)(2)(Im)(2)](BF(4))(2), space group = P2(1)/a, Z = 4, a = 11.344(1) Å, b = 17.499(3) Å, c = 15.114(3) Å, and beta = 100.17(1) degrees, and triclinic cis-[Ru(bpy)(2)(N-Im)(H(2)O)](CF(3)COO)(2).H(2)O, space group = P&onemacr;, Z = 2, a = 10.432(4) Å, b = 11.995(3) Å, c = 13.912(5) Å, alpha = 87.03(3) degrees, beta = 70.28(3) degrees, and gamma = 71.57(2) degrees, complexes show that these molecules crystallize as complexes of octahedral Ru(II) to two bidentate bipyridine ligands with two imidazole ligands or a water and an N-methylimidazole ligand cis to each other. The importance of these molecules is associated with their frequent use in the modification of proteins at histidine residues and in comparisons of the modified protein derivatives with these small molecule analogs.
Reddy
K. Bal
KB
Department of Chemistry, Rutgers, The State University of New Jersey, Piscataway, New Jersey 08855-0939.
Cho Mo
Myung-ok P.
Wishart
James F.
JF
Emge
Thomas J.
TJ
Isied
Stephan S.
SS