A ruthenium-dihydrogen putative intermediate in ketone hydrogenation

被引:100
作者
Hamilton, RJ [1 ]
Leong, CG [1 ]
Bigam, G [1 ]
Miskolzie, M [1 ]
Bergens, SH [1 ]
机构
[1] Univ Alberta, Dept Chem, Edmonton, AB T6G 2G2, Canada
关键词
D O I
10.1021/ja043339k
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The compound fac-[Ru((R)-BINAP)(H)(2-PrOH)3]+ (6) (BINAP = 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl) reacts with (R,R)-dpen (dpen = 1,2-diphenylethylenediamine) under H2 at -60 °C in 2-PrOH-d8/CD2Cl2 to generate the cationic dihydrogen putative intermediate trans-[Ru((R)-BINAP)(H)(η2-H2)((R,R)-dpen)]+ (2′) without H-D exchange between the hydrogen ligands and the solvent. A 1H NMR study concludes that the dihydrogen ligand in 2′ does not protonate 2-PrOH to a catalytically significant extent, and that 2′ requires an added base or hydride source to be an active catalyst. Copyright © 2005 American Chemical Society.
引用
收藏
页码:4152 / 4153
页数:2
相关论文
共 28 条
[1]   Mechanism of the hydrogenation of ketones catalyzed by trans-dihydrido(diamine)ruthenium(II) complexes [J].
Abdur-Rashid, K ;
Clapham, SE ;
Hadzovic, A ;
Harvey, JN ;
Lough, AJ ;
Morris, RH .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (50) :15104-15118
[2]   Ruthenium dihydride RuH2(PPh3)2((R,R)-cyclohexyldiamine) and ruthenium monohydride RuHCl(PPh3)2((R,R)-cyclohexyldiamine):: Active catalyst and catalyst precursor for the hydrogenation of ketones and imines [J].
Abdur-Rashid, K ;
Lough, AJ ;
Morris, RH .
ORGANOMETALLICS, 2000, 19 (14) :2655-2657
[3]   Catalytic cycle for the asymmetric hydrogenation of prochiral ketones to chiral alcohols:: Direct hydride and proton transfer from chiral catalysts trans-Ru(H)2(diphosphine)(diamine) to ketones and direct addition of dihydrogen to the resulting hydridoamido complexes [J].
Abdur-Rashid, K ;
Faatz, M ;
Lough, AJ ;
Morris, RH .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (30) :7473-7474
[4]   Ru(arene)(amino alcohol)-catalyzed transfer hydrogenation of ketones: Mechanism and origin of enantioselectivity [J].
Alonso, DA ;
Brandt, P ;
Nordin, SJM ;
Andersson, PG .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (41) :9580-9588
[5]   PREPARATION AND SPECTROSCOPIC PROPERTIES OF THE ETA-2-DIHYDROGEN COMPLEXES [MH(ETA-2-H2)(PR2CH2CH2PR2)2]+ (M = FE, RU, R = PH, ET) AND TRENDS IN PROPERTIES DOWN THE IRON GROUP TRIAD [J].
BAUTISTA, MT ;
CAPPELLANI, EP ;
DROUIN, SD ;
MORRIS, RH ;
SCHWEITZER, CT ;
SELLA, A ;
ZUBKOWSKI, J .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (13) :4876-4887
[6]   Hydrogen transfer to carbonyls and imines from a hydroxycyclopentadienyl ruthenium hydride: Evidence for concerted hydride and proton transfer [J].
Casey, CP ;
Singer, SW ;
Powell, DR ;
Hayashi, RK ;
Kavana, M .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (06) :1090-1100
[7]  
CLAPHAM SE, 2004, COORD CHEM REV
[8]   THE ISOTOPIC TRANS EFFECT [J].
CRABTREE, RH ;
HABIB, A .
INORGANIC CHEMISTRY, 1986, 25 (20) :3698-3699
[9]   ETA-2-DIHYDROGEN ON THE BRINK OF HOMOLYTIC CLEAVAGE - TRANS-[OS(H=H)H(PET2CH2CH2PET2)2]+ HAS SPECTROSCOPIC AND CHEMICAL-PROPERTIES BETWEEN THOSE OF THE ISOELECTRONIC COMPLEXES TRANS-[OSH(PPH2CH2CH2PPH2)2(ETA-2-H2)]+ AND REH3(PPH2CH2CH2PPH2)2 [J].
EARL, KA ;
JIA, GC ;
MALTBY, PA ;
MORRIS, RH .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (08) :3027-3039
[10]   Elongated dihydrogen complexes:: what remains of the H-H Bond? [J].
Heinekey, DM ;
Lledós, A ;
Lluch, JM .
CHEMICAL SOCIETY REVIEWS, 2004, 33 (03) :175-182