Barbato, Cinzia; Baldino, Salvatore; Ballico, Maurizio; Figliolia, Rosario; Magnolia, Santo; Siega, Katia; Herdtweck, Eberhardt; Strazzolini, Paolo; Chelucci, Giorgio; Baratta, Walter published the artcile< OsXCl(phosphine)2(diamine) and OsXCl(diphosphine)(diamine) (X = Cl, H) Complexes for Ketone Hydrogenation>, Recommanded Product: (9Z,12Z)-Methyl octadeca-9,12-dienoate, the main research area is diphoshine derivative coordinative substitution osmium chloride complex; crystal structure ferrocenediphosphino osmium diamine chloride complex; mol structure ferrocenediphosphino osmium diamine chloride complex; ferrocenediphosphino osmium diamine chloride complex preparation catalyst hydrogenation.
The Os complex trans-[OsCl2(PPh3)2(en)] (2) was prepared by reaction of [OsCl2(PPh3)3] (1a) with ethylenediamine (en), whereas the diphosphine derivatives trans-[OsCl2(dppf)(NN)] (NN = en, 3; bn = 1,4-butanediamine, 4) and trans-[OsCl2(dpbp)(en)] (5) were obtained from 1a, dppf or dpbp and the corresponding NN ligand in CH2Cl2 or toluene. An x-ray diffraction study was provided for 3. The isolation of the chiral derivatives trans-[OsCl2(diphosphine)((R,R)-dpen)] (diphosphine = dppf, 6; dpbp, 7; (R,R)-skewphos, 8) was achieved by reacting 1a with the diphosphine and (R,R)-dpen in toluene. Treatment of the precursor [Os2Cl4(P(m-tolyl)3)5] (1b) with en afforded [OsCl2(P(m-tolyl)3)2(en)] (9), while reaction of 1b with dppb and N,N-dmen gave [OsCl2(dppb)(N,N-dmen)] (10). The chiral derivatives [OsCl2(diphosphine)(NN)] (11-21) (diphosphine = (S)-MeObiphep, (R)-MeObiphep, (R)-xylMeObiphep, (R)-binap, (S)-xylbinap, (R)-xylbinap, (R,S)-Josiphos*; NN = en, (R,R)-dpen, (R)-daipen, (R,R)-dppn) were prepared from 1b and the corresponding diphosphine and NN ligands in toluene. The monohydride trans-[OsHCl(P(m-tolyl)3)2(en)] (22) was synthesized by reaction of 1b with H2 (1 atm) in the presence of NEt3, followed by addition of en in toluene. Similarly, trans-[OsHCl(dppf)(en)] (23) was synthesized from 1a, H2 and NEt3, followed by treatment with dppf and en. Complexes 2-5, 9, 10, 22 and 23 efficiently catalyzed the hydrogenation of acetophenone with H2 under low pressure (5 atm) at 60-70° in EtOH (1-2 mol% of NaOEt). The chiral derivatives 6-8 and 11-21 afforded the asym. hydrogenation of acetophenone with up to 90% ee (S/C = 10000) by combining bulky xylyl substituted MeObiphep or binap-type ligands with (R)-daipen or (R,R)-dpen ligands. Catalytic transfer hydrogenation of acetophenone was observed with 3, 6 and 7 (S/C = 2000) in iso-PrOH and in the presence of NaOiPr (2 mol%) at 60-82°.
Organometallics published new progress about Bidentate ligands Role: RCT (Reactant), RACT (Reactant or Reagent) (diamine and diphoshine derivatives). 112-63-0 belongs to class esters-buliding-blocks, and the molecular formula is C19H34O2, Recommanded Product: (9Z,12Z)-Methyl octadeca-9,12-dienoate.
Referemce:
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics