Inorganic Chemistry, Vol.41, No.24, 6267-6273, 2002
Reactions of acetonitrile coordinated to a nitrosylruthenium complex with H2O or CH3OH under mild conditions: Structural characterization of imido-type complexes
The reaction of cis-[Ru(NO)(CH3CN)(bPY)(2)](3+) (bpy = 2,2'-bipyridine) in H2O at room temperature proceeded to afford two new nitrosylruthenium complexes. These complexes have been identified as nitrosylruthenium complexes containing the N-bound methylcarboxyimidato ligand, cis-[Ru(NO)(NH=C(O)CH3)(bPY)(2)](2+), and methylcarboxyimido acid ligand, cis-[Ru(NO)(NH=C(OH)CH3)(bpy)(2)](3+), formed by an electrophilic reaction at the nitrile carbon of the acetonitrile coordinated to the ruthenium ion. The X-ray structure analysis on a single crystal obtained from CH3CN-H2O solution of cis-[Ru(NO)(NH=C(O)CH3)(bPY)(2)](PF6)(3) has been performed: C22H20.5N6O2P2.5F15Ru, orthorhombic, Pccn, a = 15.966(1) Angstrom, b = 31.839(1) Angstrom, c = 11.707(1) Angstrom, V = 5950.8(4) Angstrom(3), and Z = 8. The structural results revealed that the single crystal consisted of 1:1 mixture of cis-[Ru(NO)(NH=C(O)CH3)(bpy)(2)(2+) and cis-[Ru(NO)(NH=C(OH)CH3)(bpy)(2)](3+) and the structural formula of this single crystal was thus [Ru(NO)(NH=C(OH0.5)CH3)-(bpy)(2)](PF6)(2.5). The reaction of cis-[Ru(NO)(CH3CN)(bPY)2]3+ in dry CH3OH-CH3CN at room temperature afforded a nitrosyl ruthenium complex containing the methyl methylcarboxyimidate ligand, cis-[Ru(NO)(NH=C(OCH3)CH3)-(bpy)(2)](3+). The structure has been determined by X-ray structure analysis: C25H29N8O18Cl3Ru, monoclinic, P2(1)/c, a = 13.129(1) Angstrom, b = 17.053(1) Angstrom, c = 15.711 (1) Angstrom, beta = 90.876(5)degrees, V = 3517.3(4) Angstrom(3), and Z = 4.