Synthesis, Characterization And Biphasic Catalysiswith RuCl(η5-C5H5)(TPPMS)2

A synthetic route is reported for the water soluble complex RuCl(h⁵- C₅H₅)(TPPMS)₂(1), (TPPMS = (C₆H₅)₂P(C₆H₄-m-SO₃Na) and characterized by UV-Vis, FTIR, ¹H, ¹³C NMR and GC-MS. Complex 1 is a good catalytic precursor in biphasic media (toluene/ water) for 1-hexene hydrogenation under moderate reaction conditions (e.g. 500 psi H₂, 100°C) giving good yields of n-hexane, and smaller amounts of cis-2-hexene and trans-2-hexene. Other organic substrates (cinnamaldehyde, crotonaldehyde, cyclohexene, acetone and butylaldehyde) are hydrogenated.     

Catalytic Hydrogenation of 1-Hexene with RuCI2 (TPPMS)3(DMSO) Part II: Ionic Liquid Biphasic System

RuCl2(TPPMS)3(DMSO) (complex (I)) is very soluble in the ionic liquid 1-nbutyl-3-methylimidazolium hexafluorophosphate (BMI.PF6). Complex (I) catalyzes 1-hexene hydrogenation (500 psi H2 and 100oC) in a two-phase system, with 80% conversion in 24 h, with little substrate isomerization. Changes in catalytic behavior with temperature, pressure, time and substrate/catalyst relation are presented. Complex (I) shows good stability and can be reused several times with little activity loss. This revised version was published online in August 2006 with corrections to the Cover Date.     

Hydrolytic cleavage of Schiff bases by [RuCl2(DMSO)4]

New hexa-coordinated Ru(II) complexes of the type [RuCl₂(DMSO)₂(diamine)] (diamine = o-phenylenediamine and ethylenediamine) have been prepared by reacting cis-[RuCl₂(DMSO)₄] with Schiff bases (H₂sal-en, 1; H₂nap-en, 2; H₂sal-o-pdn, 3; H₂nap-o-pdn, 4) in a 1:1 ratio. The ligands, which were expected to act as tetradentate (N₂O₂) chelates under the normal reaction conditions, were found to undergo hydrolytic cleavage to form the diamine and the corresponding aldehyde. All the complexes have been characterized by analytical and spectroscopic (IR, electronic and¹H NMR) data. Single-crystal X-ray analysis of the complex [RuCl₂(DMSO)₂(o-pndn)] revealed that the coordination environment around the ruthenium metal consists of a N₂S₂Cl₂ octahedron.     

Preparation and structural characterization of [RuCl2(CO)2{Te(CH2SiMe3)2}2] and [RuCl2(CO){Te(CH2SiMe3)2}3]

The objective of the present work was to synthesize mononuclear ruthenium complex [RuCl₂(CO)₂{Te(CH₂SiMe₃)₂}₂] (1) by the reaction of Te(CH₂SiMe₃)₂ and [RuCl₂(CO)₃]₂. However, the stoichiometric reaction affords a mixture of 1 and [RuCl₂(CO){Te(CH₂SiMe₃)₂}₃] (2). The X-ray structures show the formation of the cis(Cl), cis(C), trans(Te) isomer of 1 and the cis(Cl), mer(Te) isomer of 2. The ¹²⁵Te NMR spectra of the complexes are reported. The complex distribution depends on the initial molar ratio of the reactants. With an excess of [RuCl₂(CO)₃]₂ only 1 is formed. In addition to the stoichiometric reaction, a mixture of 1 and 2 is observed even when using an excess of Te(CH₂SiMe₃)₂. Complex 1 is, however, always the main product. In these cases the ¹²⁵Te NMR spectra of the reaction solution also indicates the presence of unreacted ligand.     

[Ru(DMSO)4]Cl2 catalyzes the α-alkylation of ketones by alcohols

The electrophilic α-alkylation of ketones with alcohols was accomplished by a [Ru(DMSO)₄]Cl₂ catalyzed process, water being the only wasted material. The reaction can be successfully governed to produce either the expected ketones or their related alcohols only by changing the reaction conditions. When 2-aminobenzyl alcohol was used, a cyclization process took place to yield 2,3-disubstituted quinolines.     

Elucidation of inhibitors in the dimerization of acrylonitrile using [RuCl2(DMSO)4/CH3CH2COONa/DMSO/o-benzoylbenzoic acid] as catalyst

A study of inhibitors in the dimerization of acrylonitrile using the novel catalytic system of [RuCl₂(DMSO)₄/CH₃CH₂COONa/DMSO/o-benzoylbenzoic acid] was carried out by examining the effect of reaction products on the catalytic activity. 1,4-Dicyanobuta-1,3-diene (3), one of the linear dimer products of acrylonitrile, inhibited the Ru-catalyzed reaction. Methylthiomethyl o-benzoylbenzoate (8), a by-product which was produced from carboxylic acid and DMSO under the reaction conditions, also acted as an inhibitor.     

Binuclear ruthenium complexes of fluorous phosphine ligands: Synthesis, properties, and biphasic catalytic activity. Crystal structure of [Ru(μ-O2CMe)(CO)2P(CH2CH2(CF2)5CF3)3]2

The fluorocarbon soluble, binuclear ruthenium(I) complexes [Ru(μ-O₂CMe)(CO)₂L^F]₂, where L^F is the perfluoroalkyl substituted tertiary phosphine, P(C₆H₄-4-CH₂CH₂(CF₂)₇CF₃)₃, or P(CH₂CH₂(CF₂)₅CF₃)₃, were synthesized and partition coefficients for the complexes in fluorocarbon/hydrocarbon biphases were determined. Catalytic hydrogenation of acetophenone to 1-phenylethanol in benzotrifluoride at 105 °C occured in the presence of either [Ru(μ-O₂CMe)(CO)₂P(C₆H₄-4-CH₂CH₂(CF₂)₇CF₃)₃]₂ (1) or [Ru(μ-O₂CMe)(CO)₂P(CH₂CH₂(CF₂)₅CF₃)₃]₂ (2). The X-ray crystal structure of [Ru(μ-O₂CMe)(CO)₂P(CH₂CH₂(CF₂)₅CF₃)₃]₂ was determined. The compound exhibited discrete regions of fluorous and non-fluorous packing.     

The reactions of 2-benzoylpyridine with [RuHCl(CO)(PPh3)3] and [(C6H6)RuCl2]2

The reactions of [RuHCl(CO)(PPh₃)₃] and [(C₆H₆)RuCl₂]₂ with 2-benzoylpyridine have been examined, and two novel ruthenium(II) complexes – [RuCl(CO)(PPh₃)₂(C₅H₄NCOO)] and [RuCl₂(C₁₂H₉NO)₂] – have been obtained. The compounds have been studied by IR and UV–Vis spectroscopy, and X-ray crystallography. The molecular orbital diagrams of the complexes have been calculated with the density functional theory (DFT) method. The spin-allowed singlet–singlet electronic transitions of the compounds have been calculated with the time-dependent DFT method, and the UV–Vis spectra of the compounds have been discussed on this basis.     

Ruthenium complexes of the general formula [RuCl2(PHOX)2] and their catalytic activity in the Mukaiyama aldol reaction

New ruthenium phosphinooxazoline (PHOX) complexes were synthesized and applied in the Mukaiyama aldol reaction. Four ruthenium complexes of the general formula [RuCl₂(PHOX)₂] were synthesized from [RuCl₂(dmso)₄] and the corresponding PHOX ligands through thermal ligand exchange. Two of the complexes were characterized structurally. Achiral PHOX ligands gave the ruthenium complexes as single isomers, whereas chiral PHOX ligands gave a mixture of isomers and also some incomplete substitution. After activation by chloride abstraction, one of the new ruthenium complexes was applied as catalyst in the Mukaiyama aldol reaction to give silyl-protected β-hydroxyl alcohols in 74–92% isolated yields (room temperature, 18–24 h reaction time, 1 mol % catalyst loading).     

Chlorocarbonyl ruthenium(II) complexes of tripodal triphos {MeC(CH2PPh2)3}: Synthesis, characterization and catalytic applications in transfer hydrogenation of carbonyl compounds

The complex [Ru(CO)₂(triphos-κ²P)Cl₂] (1) underwent decarbonylation in dichloromethane solution under air over a period of about two weeks to afford the chelated monocarbonyl complex [Ru(CO)(triphos-κ³P)Cl₂] (2). The Single Crystal X-ray structure of 2 showed a slightly distorted metal centred complex. The catalytic activity of one of the complexes [Ru(CO)(triphos-κ³P)Cl₂] (2) was examined in the transfer hydrogenation of aromatic carbonyl compounds and was found to be efficient with conversion up to 100% in the presence of isopropanol/NaOH.     

A novel imido-transfer reaction of aldehydes with Ph3PNTs using RuCl2(PPh3)3 as catalyst

(N-Tosylimino)triphenylphosphorane (Ph₃PNTs) was found to be an efficient imido-transfer reagent for the imidation of a variety of aldehydes using RuCl₂(PPh₃)₃ as the catalyst.     

1-Heptyne semihydrogenation catalysed by [PdCl2(NH2(CH2)5CH3)2]

The [PdCl₂(NH₂(CH₂)₅CH₃)₂] complex was tested as catalyst for 1-heptyne semihydrogenation under mild conditions of temperature and pressure in homogeneous and heterogeneous systems. Species were characterized by XPS and FTIR techniques. This revised version was published online in June 2006 with corrections to the Cover Date.     

Reactions of isonitriles with [Fe3(CO)12] and [Ru3(CO)12] monitored by electrospray mass spectrometry: structural characterisation of [Fe3(CO)10(CNPh)2] and [Ru4(CO)11(μ3-η-CNPh)2(CNPh)]

The reactions of [Fe₃(CO)₁₂] or [Ru₃(CO)₁₂] with RNC (R=Ph, C₆H₄OMe-p or CH₂SO₂C₆H₄Me-p) have been investigated using electrospray mass spectrometry. Species arising from substitution of up to six ligands were detected for [Fe₃(CO)₁₂], but the higher-substituted compounds were too unstable to be isolated. The crystal structure of [Fe₃(CO)₁₀(CNPh)₂] was determined at 150 and 298 K to show that both isonitrile ligands were trans to each other on the same Fe atom. For [Ru₃(CO)₁₂] substitution of up to three COs was found, together with the formation of higher-nuclearity clusters. [Ru₄(CO)₁₁(CNPh)₃] was structurally characterised and has a spiked-triangular Ru₄ core with two of the CNPh ligands coordinated in an unusual μ₃-η² mode.     

Yb[N(SO2C8F17)2]3-catalyzed allylation of 1,3-dicarbonyl compounds with allylic alcohols in a fluorous biphase system

Allylation of 1,3-dicarbonyl compounds with allylic alcohols was successfully accomplished using rare earth metal (III) bis(perfluorooctanesulfonyl)imide [RE(NPf₂)₃, RE = La∼Lu] as catalysts in fluorous solvents. Ytterbium bis(perfluorooctanesulfonyl)imide [Yb(NPf₂)₃] catalyzes the high efficient reaction of allylation in fluorous solvents. By simple separation, fluorous phase containing only catalyst can be reused several times.     

Reaction of [(C6H6)RuCl2]2 with 7,8-benzoquinoline and 8-hydroxyquinoline

The reaction of [(C₆H₆)RuCl₂]₂ with 7,8-benzoquinoline and 8-hydroxyquinoline in methanol were performed. The obtained complexes have been studied by IR, UV–VIS, ¹H and ¹³C NMR spectroscopy and X-ray crystallography. In the reaction with 8-hydroxyquinoline the arene ruthenium(II) complex oxidized to Ru(III). The electronic spectra of the obtained compounds have been calculated using the TDDFT method. Magnetic properties of [Ru(C₉H₆NO)₃] · CH₃OH complex suggest the antiferromagnetic coupling of the ruthenium centers in the crystal lattice. EPR spectrum of [Ru(C₉H₆NO)₃] · CH₃OH compound indicates single isotropic line only characteristic for Ru³⁺ with spin equal to 1/2.     

Selective formation of trans and cis(CH3CN) isomers of [Ru(bpy)(CO)2(CH3CN)2] (bpy=2,2-bipyridine) from [Ru(CO)2(CH3CN)3]2(PF6)2 using an electrochemical oxidation step

The selective in situ synthesis of trans and cis(CH₃CN)-[Ru(bpy)(CO)₂ (CH₃CN)₂]²⁺ isomers from the same [Ru(CO)₂ (CH₃CN)₃]₂²⁺ dimer precursor but using either an electrochemical-chemical or chemical-electrochemical process is described.     

Synthesis, structure and hydrogenation catalytic activity of [Ru3(μ3,η-ampy)(μ,η:η-PhC=CHPh)(CO)6(PPh3) (Hampy = 2-amino-6-methylpyridine)

The compound [RU₃(μ₃,η²- -ampy)(μ₃η¹:η²-PhC=CHPh)(CO)₆(PPh₃)₂] (1) (ampy = 2-amino-6-methylpyridinate) has been prepared by reaction of [RU₃(η-H)(μ₃,η²- ampy) (μ,η¹:η²-PhC=CHPh)(CO)₇(PPh₃)] with triphenylphosphine at room temperature. However, the reaction of [RU₃(μ-H)(μ₃, η² -ampy)(CO)₇(PPh₃)₂] with diphenylacetylene requires a higher temperature (110°C) and does not give complex 1 but the phenyl derivative [RU₃(μ₃,η²-ampy)(μ,η ¹:η² -PhC=CHPh)(μ,-PPh₂)(Ph)(CO)₅(PPh₃)] (2). The thermolysis of complex 1 (110°C) also gives complex 2 quantitatively. Both 1 and 2 have been characterized by0 X-ray diffraction methods. Complex 1 is a catalyst precursor for the homogeneous hydrogenation of diphenylacetylene to a mixture of cis- and trans -stilbene under mild conditions (80°C, 1 atm. of H₂), although progressive deactivation of the catalytic species is observed. The dihydride [RU₃(μ-H)₂(μ ₃,η²-ampy)(μ,η¹:η²- PhC=CHPh)(CO)₅(PPh₃)₂] (3), which has been characterized spectroscopically, is an intermediate in the catalytic hydrogenation reaction.     

Reaction of [CpRu(CH3CN)3]PF6 with bidentate ligands: structural characterization of [{CpRu(CH3CN)2}2(μ-η-dppe)](PF6)2 [dppe=1,2-bis(diphenylphosphino)ethane]

The reaction of [CpRu(CH₃CN)₃]PF₆ with the bidentate ligands L-L=1,2-bis(diphenylphosphino)ethane, dppe, and (1-diphenylarsino-2-diphenylphosphino)ethane, dpadppe, affords mononuclear or dinuclear complexes of formula [CpRu(η²-L-L)(CH₃CN)]PF₆, [{CpRu(CH₃CN)₂}₂(μ-η^1:1-L-L)](PF₆)₂ and [{CpRu(CH₃CN)}₂(μ-η^1:1-L-L)₂](PF₆)₂ (L-L=dppe, dpadppe). All of the compounds are characterized by microanalysis and NMR [¹H and ³¹P{¹H}] spectroscopy. The crystal structure of [{CpRu(CH₃CN)₂}₂(μ-η^1:1-dppe)](PF₆)₂ has been determined by X-ray diffraction analysis. The complex exhibits a dppe ligand bridging two CpRu(CH₃CN)₂ fragments.     

RuCl2[P(C6H5)3]2-(R,R)-DPEN催化萘乙酮不对称加氢反应

 合成了(R,R)-1,2-二苯基乙二胺((R,R)-DPEN)、 钌和三苯基膦的三元配合物RuCl2[P(C6H5)3]2-(R,R)-DPEN, 并将其用于萘乙酮的不对称加氢反应. 考察了碱/催化剂的摩尔比、反应温度和氢气压力等对催化活性和对映选择性的影响. 结果表明,多种因素对反应的转化率和对映选择性均有影响. 在萘乙酮:(CH3)3COK:催化剂摩尔比为 50000:450:1, 氢气压力为4 MPa, 反应温度为25 ℃的条件下,反应16 h时,萘乙酮生成α-萘乙醇的产率和对映选择性分别达到了100%和83%.