Dehydrogenation of alcohols and hydrogenation of aldehydes using homogeneous ruthenium catalysts

Half-sandwich ruthenium(II) complexes of aminophosphines: synthesis, structures and catalytic applications in C–C coupling reactions between styrenes and diphenyldiazomethane

“…The reactions of aminobis(phosphines), Ph 2 PN(R)-PPh 2 (R 0/Et, n Pr, i Pr, n Bu) with equimolar quantity of [CpRuCl(PPh 3 ) 2 ] afford cationic complexes, [CpRu-(PPh 3 )(Ph 2 PN(R)PPh 2 -kP,kP)]Cl (R 0/Et [20],7;n Pr,8;i Pr,9;n Bu,10) in 50Á/60% yield (Scheme 2). The 31 P-NMR spectra of complexes 7 Á/10 show triplets for PPh 3 around 44Á/45 ppm and doublets for PPh 2 in the range of 80Á/83 ppm with 2 J PRuP couplings of 35 Hz.…”

“…Yield: 39% (0.02 g, 0.027 mmol). (R 0/Et,7;n Pr,8;i Pr,9;n Bu,10) To a stirring solution of CpRuCl(PPh 3 ) 2 (0.050 g, 0.069 mmol) in toluene (5 ml) was added a solution of PPh 2 N(R)PPh 2 (R 0/Et, n Pr, i Pr, n Bu) (0.069 mmol) also in toluene (5 ml) and the reaction mixture was heated to 100 Á/105 8C for 10 h (12 h when R 0/ i Pr). The yellow solid precipitated out was filtered and washed with Et 2 O (3)/5 ml) and crystallized from CH 2 Cl 2 Á/nhexane (2:1) mixture to give analytically pure products, 7 Á/10.…”

Synthesis and Reactivity of Ru(NHC)(dppp)(CO)H2 and Ru(NHC)(dppp)(CO)HF Complexes: C–H and C–F Activation

“…C 6 F 6 , C 6 F 5 H, C 6 F 5 CF 3 , C 6 F 4 HCF 3 , C 5 F 5 N, C 5 F 4 HN and Et 3 SiH were dried with activated molecular sieves (3 Å) and stored under argon. [Ru(PPh 3 ) 3 (CO)HF], [9] [Ru(PPh 3 )(dppp)(CO)H 2 ], [37] [Ru-(IMes)(dppp)(CO)H 2 ] (4), [5] IMes, [38] IEt 2 Me 2 [39] and ICy [40] were prepared via literature methods. NMR spectra were recorded on Bruker Avance 400 and 500 spectrometers at 25°C unless otherwise stated, with 1 H and 13 C chemical shifts referenced to internal solvent references.…”

Hydrogenation and Reductive Amination of Aldehydes using Triphos Ruthenium Catalysts

“…In addition, homogeneous catalysis used in hydrogenation can find applications in transformations in which alternative heterogeneous catalysts fail to deliver satisfactory chemoselective reductions. Simple phosphine ruthenium complexes were reported to be capable homogeneous catalysts for aldehyde hydrogenation in the late 1970s and early 1980s . The well‐established phosphine ruthenium diamine catalysts developed by Noyori et al.…”

“…Simple phosphine ruthenium complexes were reportedt ob ec apable homogeneous catalysts for aldehyde hydrogenation in the late 1970s and early 1980s. [2][3][4][5][6] The well-established phosphine ruthenium diamine catalysts developed by Noyori et al gave significant improvements in activity for carbonyl reduction under basic reactionc onditions, although the requiremento f base, in some cases, can also be regarded as al imitation of this technology. [7,8] An umber of refinements and advances have been applied to address these limitations, for example, the development of RuH(h 1 -BH 4 )c omplexes reported by Noyorie tal.…”