8-Quinolinolato complexes of ruthenium(II) and (III)

Reduction of RuQ3 (1a, Q = 8-quinolinolato) with Zn/Hg in the presence of various π-acceptor ligands in ethanol affords RuQ2L2 (L2 = (dimethylsulfoxide)2 (2); (4-picoline)2 (3); N,N′-dimethyl-1,4-diazabuta-1,3-diene, dab (4); cyclooctadiene, COD (5); norborna-2,5-diene, nbd (6)). Compound 6 is isolated as an equimolar mixture of cis,trans (6a) and trans,cis (6b) isomers, which can be separated by column chromatography. DFT calculations have been performed on 6a and 6b. Oxidation of 3 and 6b affords the corresponding ruthenium(III) species 7 and 8, respectively. The structures of 2, 3, 4 and 6 have been determined by X-ray crystallography.

Reduction of RuQ3 in the presence of various π-acceptor ligands (L) such as dmso, 4-picoline and alkenes affords RuIIQ2L2. Two geometric isomers of RuQ2(nbd) have been isolated (nbd = norborna-2,5-diene) and structurally characterized; DFT calculations have also been performed on these two compounds. Oxidation of ruthenium(II) (for L = picoline and norbornadiene) gives the corresponding ruthenium(III) species.Figure optionsDownload as PowerPoint slide