14564-35-3Relevant academic research and scientific papers
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.
Olefin ligands II. Syntheses of 2,6-diallylpyridine (DAP) complexes of iridium(I), ruthenium(II), palladium(II) and platinum(II); crystal structures of and
Vasapollo, Giuseppe,Nobile, Cosimo Francesco,Latronico, Mario,Lanfranchi, Maurizio,Pellinghelli, Maria Angela
, p. 429 - 440 (1987)
The tridentate ligand 2,6-diallylpyridine (DAP) has been used to synthesize novel complexes of iridium(I), ruthenium(II), palladium(II) and platinum(II) of formulae , , ClO4, , PdCl2(DAP)2>, .All the complexes have been characterized by elemental analysis.IR, and 1H NMR spectroscopy.The molecular structures of and have been determined by single-crystal X-ray diffraction studies.Crystals of the ruthenium complex are orthorhombic, space group Pbca, with Z=8 in a unit cell of dimensions a 11.492(5), b 18.942(3), c 23.083(9) Angstroem.Crystals of the palladium complex are triclinic, space group with Z=1 in a unit cell of dimensions a 7.950(4), b 8.745(4), c 9.578(4) Angstroem, α 113.02(3), β 90.75(3), γ 116.65(3)o.Both structures were solved by Patterson and Fourier methods and refined by blocked full-matrix least-squares to R=0.0528 for 2742 observed reflections in the first complex and by full-matrix least-squares to R=0.0252 for 1948 observed reflections in the second.In the octahedral ruthenium complex, DAP acts as a tridentate ligand adopting a mer configuration and the phosphine ligand is trans to the pyridinic nitrogen, while in the trans square-planar palladium complex DAP acts as a monodentate N-donor ligand.
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
On the reactivity of tris(triphenylphosphine)triruthenium enneacarbonyl
Piacenti,Bianchi,Benedetti,Braca
, p. 1815 - 1817 (1968)
By reaction of [Ru(CO)3P(C6H5)3]3 with CO, Ru(CO)4P(C6H5)3 has been prepared from which, with halogens (X = Cl, Br, I) or CHCl3, [RuX2(CO)2P(C6H5)3] 2 complexes were obtained. These last compounds could also be formed from [Ru(CO)3P-(C6H5)3]3 and halogens. From the ir spectral data a structure with bridging halogens is suggested for the dimeric compounds [RuX2(CO)2P(C6H5)3] 2. [Os(CO)3P(C6H5)3]3 reacts with CO with displacement of P(C6H5)3 and formation of [Os(CO)4]3.
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].
Bis(alkynyl), metallacyclopentadiene, and diphenylbutadiyne complexes of ruthenium
Hill, Anthony F.,Rae, A. David,Schultz, Madeleine,Willis, Anthony C.
, p. 1325 - 1338 (2008/10/09)
Heating diphenylbutadiyne with [Ru(CO)2(PPh3) 3] or [Ru(CO)3(PPh3)2] in toluene under reflux provides respectively the ruthenacyclopentadiene [Ru{κ2-CR=CPhCPh=CR}(CO)2(PPh3) 2] (R = C≡CPh) or the cyclopentadienone complex [Ru{η4-O=CC4Ph2R2}(CO) 2(PPh3)], the latter via [2 + 2 + 1] alkyne and CO cyclization. The bis(alkynyl) complex cis,cis,trans-[Ru(C≡CPh) 2(CO)2(PPh3)2] is not formed in either of these reactions but is the product of the reaction of [RuCl 2(CO)2(PPh3)2] with LiC≡CPh or of cis,-mer-[Ru(C≡CPh)2(CO)(PPh3)3] with CO. Although the bis(alkynyl) complex does not undergo reductive elimination to provide the diyne complex, thermolysis of cis,cis,trans-[Ru(C≡CPh) (HgC≡CPh)(CO)2-(PPh3)2] (obtained from [Ru(CO)2(PPh3)3] and [Hg(C≡CPh) 2]) provides a noninterconvertible 1:1 mixture of cis,cis,trans-[Ru(C≡CPh)2(CO)2(PPh3) 2] and [Ru(η-PhC≡CC≡CPh)(CO)2(PPh 3)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.
Binuclear ruthenium macrocycles formed via the weak-link approach
Khoshbin, Meisa S.,Ovchinnikov, Maxim V.,Mirkin, Chad A.,Zakharov, Lev H.,Rheingold, Arnold L.
, p. 496 - 501 (2008/10/09)
The weak-link approach for the synthesis of metallomacrocycles has been used to synthesize a series of novel Ru(II) macrocycles in high yield. RuCl2(PPh3)3 has been reacted with two different phosphino-alkyl-ether hemilabile ligands, 1,4-(PPh2(CH 2)2O)2C6H4 and 1,4-(PPh2(CH2)2OCH2) 2C6H4. The hemilabile bidentate ligand coordinates to Ru(II) centers through both the P and O atoms to form bimetallic condensed intermediates . The weak Ru-O bonds have been selectively cleaved with CO, 1,2-diaminopropane, and pyridine to yield large open macrocycles. This is the first example of the weak-link approach employed to synthesize macrocycles with Ru, and metal centers in general that have more than four coordination sites.
A facile route to carbonylhalogenometal complexes (M = Rh, Ir, Ru, Pt) by dimethylformamide decarbonylation
Serp, Philippe,Hernandez, Marc,Richard, Brigitte,Kalck, Philippe
, p. 2327 - 2336 (2007/10/03)
Dimethyl formamide (DMF) can be a convenient source of the carbonyl ligand in the coordination chemistry of rhodium, ruthenium, iridium, and platinum. We have undertaken a thorough study concerning the course of this reaction. In a first step, DMF-containing complexes are produced, which is usually accompanied by chloride redistribution. Then, upon refluxing, carbonyl species in the same oxidation state are obtained, presumably as a result of HCl-mediated DMF decomposition. Provided that water levels are kept low, reduction can occur to provide the complexes [NH2(CH3)2][RhCl2(CO) 2], [NH2(CH3)2][RuCl3(CO) 2(DMF)], [RuCl2(CO)2(DMF)2], and [NH2(CH3)2][IrCl2(CO) 2]. In the case of platinum, reduction is not effective and [NH2(CH3)2][PtCl3(CO)] is obtained. No carbonylpalladium species can be synthesized in this way, the reaction producing copious amounts of colloidal metal. Adding phosphanes to these chlorocarbonyl-containing solutions allows easy, one-step syntheses of a variety of complexes.
