Neutral η6-arene ruthenium complexes with monodentate P-donor ligands: Activation in the transfer hydrogenation reaction
2012
Abstract Five Ru(II) neutral complexes C of the type [RuCl 2 (η 6 -arene)( P )] ( P = monodentate phosphorus ligand) have been prepared: C1 (arene = p -cymene, P = PPh 3 ); C2 (arene = p -cymene, P = ( R )-Monophos); C3 (arene = p -cymene, P = ( S )-Ph-Binepine); C4 (arene = benzene, P = PPh 3 ); and C5 (arene = benzene, P = ( S )-Ph-Binepine). These complexes have been screened as catalytic precursors in the transfer hydrogenation of acetophenone with 2-propanol. Under optimised conditions at 82 °C complexes C1 and C4 provide full conversion in less than 20 min at a [Ru]:substrate ratio of 1:200. With the chiral complexes C2 and C3 good TOF values have been reached but with low enantioselectivities. The activation of the catalytic precursor has been studied. Based on NMR evidence, a mechanism in which the catalytically active species is a Ru monohydride complex arising from the reaction of the catalyst precursor C with 2-propanol in the presence of a base is suggested. The reaction shows different sensitivity towards excess of phosphine: whereas excess of PPh 3 slows down the reaction severely, excess of ( S )-Ph-Binepine does not cause such a sharp effect. An excess of chloride ion affects the activation of the precursor C .
Keywords:
- Correction
- Source
- Cite
- Save
- Machine Reading By IdeaReader
37
References
28
Citations
NaN
KQI