30352-62-6

Upstream product

• 27599-25-3 dihydridotetrakis(triphenylphosphine)ruthenium 
• 7727-37-9 nitrogen 
• 50982-12-2 dichloro(1,5-cyclooctadiene)ruthenium(II) 
• 603-35-0 triphenylphosphine 
• 78-92-2 iso-butanol 
• 1352709-70-6 {RuHCl(P(C₆H₅)3)3}*CH₃C₆H₅ 

Relevant academic research and scientific papers

Efficient and selective aerobic oxidation of alcohols into aldehydes and ketones using ruthenium/TEMPO as the catalytic system

The combination of RuCl2(PPh3)3 and TEMPO affords an efficient catalytic system for the aerobic oxidation of a variety of primary and secondary alcohols, giving the corresponding aldehydes and ketones, in >99% selectivity in all cases. The Ru/TEMPO system displayed a preference for primary vs secondary alcohols. Results from Hammett correlation studies (ρ = -0.58) and the primary kinetic isotope effect (kH/kD = 5.1) for the catalytic aerobic benzyl alcohol oxidations are inconsistent with either an oxoruthenium (O=Ru) or an oxoammonium based mechanism. We postulate a hydridometal mechanism, involving a "RuH2(PPh3)3" species as the active catalyst. TEMPO acts as a hydrogen transfer mediator and is either regenerated by oxygen, under catalytic aerobic conditions, or converted to TEMPH under stoichiometric anaerobic conditions.

Catalytic activity of dihydride ruthenium complexes in the hydrogenation of nitrogen containing heterocycles

The catalytic activity of the dihydride ruthenium complexes, RuH 2(CO)2(PnBu3)2, RuH 2(CO)2(PPh3)2 and RuH 2(PPh3)4, in the hydrogenation of nitrogen containing heterocycles has been tested by analyzing the influence of reaction parameters such as temperature, hydrogen pressure, catalyst concentration, on the rate and regioselectivity of the reaction. RuH2(PPh 3)4 shows a better catalytic activity with an 86.7% conversion of quinoline after 24 h at 100°C under a hydrogen pressure of 25 bar, while RuH2(CO)2(PPh3)2 and RuH2(CO)2(PnBu3)2 in the same conditions give a conversion of 37.1% and 35.6%, respectively. These results are confirmed by the reaction rate of the hydrogenation of quinoline, since the Kc in the presence of RuH2(PPh3) 4 (1.46 × 10-5 s-1) is higher than others (6.37 × 10-6 s-1 for RuH2(CO) 2(PPh3)2 and 6.36 × 10-6 s-1 for RuH2(CO)2(PnBu 3)2). Noteworthy is the selectivity of these catalytic systems in the hydrogenation of quinoline: in all tests the three catalysts lead to 1,2,3,4-tetrahydroquinoline as the major product, furthermore this compound is the only formed in the presence of RuH2(CO)2(PPh 3)2. The selectivity is affected by the presence of an acid (CH3COOH) or a base (NnBu3) in the reaction media. The complex RuH2(PPh3)4 is catalytically active, even if in a minor extent, in the hydrogenation of isoquinoline, pyridine and 2-methylpyridine. The basicity of the substrate and steric hindrance around the nitrogen atom show a great influence on the conversion. The results obtained suggest that the catalytic system activates a heterocyclic ring through the coordination of the heteroatom to the metal centre of the complexes.

Convenient synthesis of ruthenium(II) dihydride phosphine complexes Ru(H)2(PP)2 and Ru(H)2(PR3)x (x = 3 and 4)

A novel and convenient one-pot synthesis of ruthenium(II) dihydride phosphine complexes from the air-stable [RuCl2(COD)]x, the appropriate phosphine, and NaOH in sec-butyl alcohol under argon at 80 °C is reported. A series of chelating (dcpm, dcpe, dppe, dppb, dppp, dppf, and depe) and monodentate phosphine (PEt3 and PPh3) complexes have been synthesized using this methodology. The crystalline products are isolated in high yield. These dihydride complexes have been shown to be useful precursors to cationic dihydrogen hydride complexes, some of which exhibit significant activity as hydrogenation catalysts.

Roles of Neutral and Anionic Ruthenium Polyhydrides in the Catalytic Hydrogenation of Ketones and Arenes

fac-- (1) and (3) have been shown to coexist through the equilibrium 1 + ROH 3 + RO-, for which Keq ca. 0.13 for cyclohexanol in THF.The following reactions have been characterized: (1) 3 +