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. © 2012 Elsevier B.V.

Neutral η 6-arene ruthenium complexes with monodentate P-donor ligands: Activation in the transfer hydrogenation reaction

Mannu A.;
2012-01-01

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. © 2012 Elsevier B.V.
2012
363-364
49
57
Acetophenone reduction; Induction period; Ruthenium arene complexes; Transfer hydrogenation
Grabulosa A.; Mannu A.; Alberico E.; Denurra S.; Gladiali S.; Muller G.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2318/1735717
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