663626-25-3Relevant academic research and scientific papers
Carbonyl-Carboxylato-Ruthenium Complexes Incorporating Diimine Ligands and Unexpected Cyclometalation of Carboxylate Ligands
Pearson, Pauline,Kepert, Christopher M.,Deacon, Glen B.,Spiccia, Leone,Warden, Andrew C.,Skelton, Brian W.,White, Allan H.
, p. 683 - 691 (2008/10/09)
We report two new synthetic routes to the dinuclear Ru(I) complexes, [RuI2(RCO2)(CO)4(N/N) 2]+ (N/N = 2,2′-bipyridine or 1,10-phenanthroline derivatives) that use RuCl3·3H2O as a starting material. Direct addition of the bidentate diimine ligand to a methanolic solution of [Ru(CO)2Cl2]n and sodium acetate yielded a mixture of [RuI2(MeCO2)(CO) 4(N^N)2]+ (N^N = 4,4′-dmbpy, and 5,6-dmphen), and [RuII(MeCO2)2(CO) 2(N^N)] (N^N = 4,4′-dmbpy and 5,5′-dmbpy). Single-crystal X-ray studies confirmed that the Ru(II) complexes had a trans-acetate-cis-carbonyl arrangement of the ligands. In contrast, the use of sodium benzoate resulted in the unexpected formation of a Ru-C bond producing ortho-cyclometalated complexes, [RuII(O2CC 6H4)(CO)2(N^N)], where N^N = bpy or phen. A second approach used ligand exchange between a bidentate ligand (N^N) and the pyridine ligands of [RuI(RCO2)(CO)2(py)] 2 to convert these neutral complexes into [RuI 2(RCO2)(CO)4(N^N)2]+. This method, although it involved more steps, was applicable for a wider variety of diimine ligands (R = Me and N^N = 4,4′-dmbpy, 5,5′-dmbpy, 5,6-dmphen; R = Ph and N^N = bpy, phen, 5,6-dmphen).
