14564-35-3Relevant articles and documents
METHANOL AS A HYDROGEN DONOR IN REACTIONS HOMOGENEOUSLY CATALYSED BY RUTHENIUM AND RHODIUM COMPLEXES
Smith, Thomas A.,Maitlis, Peter M.
, p. 385 - 396 (1985)
Under suitable conditions methanol can act as a hydrogen donor towards organic substrates, especially for the reduction of ketones to alcohols.A variety of complexes of rhodium, iridium, ruthenium, and osmium have been shown to be active for this reaction; the highest activity observed so far is that of t-phosphine-ruthenium-chloride systems such as .In all the reactions the methanol is oxidised to methyl formate; some carbon dioxide is also formed.Cyclohexanone is reduced to cyclohexanol, methyl vinyl ketone and mesityl oxide to the corresponding saturated ketones, and 4-t-butylcyclohexanone to a 4/1 mixture of the trans and cis 4-t-butylcyclohexanols; aldehydes are reduced with more difficulty and cyclohexene is comparatively unreactive.Possible mechanisms for the reaction are discussed in the light of observations of changes in the catalyst precursors that take place during the rections.The reactions with methanol are also contrasted with those in wich ethanol is used as hydrogen donor.
Pandey, D. S.,Agarwala, U. C.
, p. 197 - 200 (1989)
Ruthenium(II) diphosphine(phosphine)/imine/amine/CO complexes as efficient catalysts in transfer hydrogenation of ketones
Ge, Sai,Zhang, Jin,Zhao, Jianguo,Ulhaq, Imran,Ma, Guibin,McDonald, Robert
, p. 7 - 14 (2019)
Treatment of [RuCl2(CO)2]n with different phosphine ligands, four Ru(II) complexes of cis-, cis-, trans- RuCl2(CO)2L2 (L = PH(C6H11)2 (1), PPh3 (2), PPh2(C6F5) (3) and PMe3 (4)), in which 1 and 3 are novel complexes, have been generated in methylene chloride and isolated as pure compound in solid. In CH2Cl2 mixed 1:1 molar ratio of RuCl2(PPh3)3 and 1,1′-bis(diphenylphosphine)ferrocene (DPPF), and further reacted with quantitative 2-aminopyridine (ampy), 2-picolylamine (picam) and pyridine ligands, the complexes of RuCl2(DPPF)(ampy) (5), RuCl2(DPPF)(picam) (6) and RuCl2(DPPF)(Py)2 (7) were generated in situ and isolated in solid. All complexes are fully characterized by multinuclear NMR (1H, 13C, 31P and 19F), element analysis and FTIR spectroscopies. Meanwhile, the single crystal structures of 1 and 8 complexes were determined by X-ray crystallography. The observed IR and crystal data of 1 ～ 4 clearly indicate that different phosphine donor ligands occupying trans axis position of Ru(II)Cl2(CO)2 skeleton can affect the coordination carbonyl C-O bond distance (1.143(3) ? (1), 1.135(3) ? (4) and 1.131(5) ? (2)), and this interaction can be quantitatively detected by its FTIR vibration frequencies. The homogeneous hydrogenation transfer catalytic reactivity of so-synthesized complexes has been tested in a basic 2-propanol solution and they indeed perform the catalytic activities in different behavior, e.g. complexes 1 and 6 are the most active catalysts and represent maximum conversion yield (1: 90.4% and 6: 90.0%) and turnover frequency (TOF) (1 18.84 h?1 and 6 37.5 h?1) at our tested experimental condition of these two types of structural complexes, which are discussed in the details.
Kinetics and mechanism of the hydrogenolysis of a ruthenium(II) acyl complex
Joshi,James
, p. 199 - 205 (1990)
The kinetics of the solution hydrogenolysis of the six-coordinate Ru(II) acyl complex RuCl(COR)(CO)2(PPh3)2, where R = norbornenyl, to give RuHCl(CO)2(PPh3)2 and RCHO reveal that the proces
Reactions of [Ru(CO)2(PPh3)3] with alkynylphosphonium salts: A phosphinoallene complex
Ang, Wee Han,Cordiner, Richard L.,Hill, Anthony F.,Perry, Tamara L.,Wagler, Joerg
, p. 5568 - 5574 (2009/12/08)
[Ru(CO)2(PPh3)3] reacts with either HC=CCH2Br or [HC=CCH2SMe2]Br to provide the σ-allenyl complex [Ru(CH=C=CH2)Br(CO)2(PPh 3)2]; however, with [HC=CCH2PPh3]Br, the salt [Ru(γ2-H2C=C=CHPPh3)(CO) 2(PPh3)2]Br is obtained, which may be described as a complex of a phosphonioallene on the basis of crystallographic data for [Ru(γ2-H2C=C=CHPPh3)(CO) 2(PPh3)2]2Br(PF6) and a comparison of spectroscopic data with those for the simple allene complex [Ru(γ2-H2C=C=CH2)(CO) 2(PPh3)2].
Synthesis, characterization, reactivity and theoretical studies of ruthenium carbonyl complexes containing ortho-substituted triphenyl phosphanes
Moreno, M. Andreina,Haukka, Matti,J??skel?inen, Sirpa,Vuoti, Sauli,Pursiainen, Jouni,Pakkanen, Tapani. A.
, p. 3803 - 3814 (2007/10/03)
A series of ruthenium o-phosphane complexes was synthesized and characterized. The reactivity of the prepared complexes was studied by using them as catalysts for the hydroformylation of 1-hexene. The activities depended on the binding mode of the phosphane and on the strength of the ruthenium-phosphane interaction. Strongly coordinated chelating [2-(dimethylamino)phenyl]-(diphenyl) phosphane and [2-(methylthio)phenyl]- (diphenyl) phosphane showed poor activity, while weakly chelated [2-(methoxy)phenyl]-(diphenyl) phosphane and non-chelating phosphanes such as [2-(methyl)phenyl]-(diphenyl) phosphane or [2-(ethyl)phenyl]-(diphenyl) phosphane led to higher activities.
