107656-24-6Relevant academic research and scientific papers
2,2,2-Trifluoroethanol-assisted imine hydrogenation by a Ru-monohydride
Scodeller, Ivan,Salvini, Antonella,Manca, Gabriele,Ienco, Andrea,Luconi, Lapo,Oberhauser, Werner
, p. 242 - 247 (2015)
The trans heterodiphosphane Ru-based compound of the formula [Ru(OAc)2(CO)2(PnBu3)(PPh3)] proved to be a suitable precatalyst for imine hydrogenation in 2,2,2-trifluoroethanol (TFE) without the addition of an external base. High-pressure (HP) NMR investigations combined with a DFT-study, carried out on a related model precatalyst, were indicating the formation of a cationic Ru-monohydride-2,2,2-trifluoroethanol (TFE) species that catalyzes the imine hydrogenation by a TFE-assisted outer-sphere reaction mechanism.
Mononuclear ruthenium complexes containing two different phosphines in trans position: II. Catalytic hydrogenation of C{double bond, long}C and C{double bond, long}O bonds
Salvi, Luca,Salvini, Antonella,Micoli, Francesca,Bianchini, Claudio,Oberhauser, Werner
, p. 1442 - 1450 (2007/10/03)
Bis(acetate) ruthenium(II) complexes of the general formula Ru(CO)2(OAc)2(PnBu3) [P(p-XC6H4)3] (OAc = acetate, X = CH3O, CH3, H, F or Cl), containing different phosphine ligands trans to PnBu3, have been employed as catalyst precursors for the hydrogenation of 1-hexene, acetophenone, 2-butanone and benzylideneacetone. For comparative purposes, analogous reactions have been performed using the homodiphosphine precursors Ru(CO)2(OAc)2(PnBu3)2 and Ru(CO)2(OAc)2(PPh3)2. The catalytic activity of the heterodiphosphine complexes depends on the basicity of the triarylphosphine trans to PnBu3 as this factor controls, inter alia, the rate of formation of hydride(acetate), Ru(CO)2(H)(OAc)(PnBu3)[P(p-XC6 H4)3], or dihydride, Ru(CO)2(H)2(PnBu3)[(p-XC 6H4)3], complexes, by hydrogenation of the bis(OAc) precursors. The catalytic hydrogenation of the C{double bond, long}C double bond is best accomplished by homodiphosphine dihydride catalysts, while heterodiphosphine monohydrides are more efficient catalysts than the homo- and heterodiphosphine dihydrides for the reduction of the keto C{double bond, long}O bond.
Chemoselective hydrogenation of α,β-unsaturated ketones to allylic alcohols, catalyzed by a mononuclear ruthenium complex containing trans PnBu3 and PPh3 ligands
Micoli, Francesca,Oberhauser, Werner,Salvini, Antonella,Bianchini, Claudio
, p. 2334 - 2341 (2008/01/27)
The ruthenium(II) bis(acetate) complex Ru(CO)2(OAc)2(PnBu3) (PPh3) (OAc = acetate) containing two different trans phosphine ligands, has been employed as pre-catalyst for the chemoselective hydrogenation of α,β-unsaturated ketones to allylic alcohols. Analogous catalytic reactions with the homodiphosphine pre-catalysts Ru(CO)2(OAc)2(PnBu3) 2 and Ru(CO)2(OAc)2(PPh3)2 gave lower conversions and selectivities. Batch catalytic reactions and operando high-pressure NMR experiments have contributed to establish that the hydrogenation of the C{double bond, long}O group is performed by the heterodiphosphine monohydride RuH(CO)2(OAc)(PnBu3)(PPh3) generated in situ by hydrogenation of the bis(OAc) precursor. PPh3 unfastening from this monohydride complex is an essential condition for the occurrence of catalytic activity.
