55978-89-7Relevant academic research and scientific papers
Preparation of RuCH2PMe2(PMe3)3Cl, Ru(CH2PMe2)2(PMe3)2, and Rh2(CH2PMe2)2(PMe3) 4 and their reactions with hydrogen
Mainz, Vera V.,Andersen, Richard A.
, p. 675 - 678 (1984)
The cis-Ru(O2CMe)Cl(PMe3)4, prepared by phosphine exchange on Ru(O2CMe)Cl(PPh3)3, reacts with 1 or 2 molar equiv of LiN(SiMe3)2 to give the metallacycle Ru(CH2PMe2)Cl(PMe3)3. The metallacycle reacts with hydrogen to give cis-RuHCl(PMe3)4. The cis-Ru(O2CMe)2(PMe3)4, prepared by phosphine exchange on Ru(O2CMe)2(PPh3)2, reacts with 2 molar equiv of LiN(SiMe3)2 to give the spirocycle Ru(CH2PMe2)2(PMe3)2. The spirocycle reacts with hydrogen to give cis-RuH2(PMe3)4. The cation [Rh(PMe3)4][O2CMe], prepared by phosphine exchange on Rh(O2CMe)(PPh3)3, reacts with LiN(SiMe3)2 to give the dimeric Rh2(CH2PMe2)2(PMe3) 4. The latter reacts with hydrogen to give fac-RhH3(PMe3)3. Thus, LiN(SiMe3)2 acts as a strong base rather than a nucleophile in these reactions.
Liquid-Phase Dehydrogenation of Methanol with Homogeneous Ruthenium Complex Catalysts
Itagaki, Hiroaki,Shinoda, Sumio,Saito, Yasukazu
, p. 2291 - 2294 (2007/10/02)
Catalytic dehydrogenation of methanol proceeded with homogeneous ruthenium(II) complexes, yielding formaldehyde and dihydrogen as primary products under refluxing conditions of the solution.The effects of additives on the initial reaction rate were examined for lithium chloride, lithium acetate, acetic acid and ethyldiphenylphosphine.A catalyst complex, , was deactivated gradually by the displacement of the bidentate OAc ligand with H and CO ligands during the reaction.These cis-disposed sites would be used for splitting the C-H bonds.A catalytic reaction cycle is proposed, in which such processes are included as solvolysis of the catalyst complex, β-H elimination from the OCH3 ligand and attack of acetic acid on the hydride intermediate to generate dihydrogen.
