14284-93-6

Basic information

• Product Name: Ruthenium acetylacetonate
• Synonyms: RUTHENIUM(III) 2,4-PENTANEDIONATE;RUTHENIUM(III) ACETYLACETONATE;TRIS(ACETYLACETONATO)RUTHENIUM(III);TRIS(PENTANE-2,4-DIONATO)RUTHENIUM(III);2,4-PENTANEDIONE, RUTHENIUM(III) DERIVATIVE;4-pentanedionato-o,o’)-tris((oc-6-11)-rutheniu;Ruthenium(III) 2,4-pentanedionate~Tris(acetylacetonato)ruthenium(III)~Tris(2,4-pentanedionato)ruthenium(III);Rutheniumacetylacetonateredbrownxtl
• CAS NO: 14284-93-6
• Molecular Formula: C₁₅H₂₁O₆Ru
• Molecular Weight: 398.39
• EINECS: 238-193-0
• Product Categories: Catalysts for Organic Synthesis;Classes of Metal Compounds;Homogeneous Catalysts;Metal Complexes;Ru (Ruthenium) Compounds;Synthetic Organic Chemistry;Transition Metal Compounds;metal beta-diketonate complexes;chemical reaction,pharm,electronic,materials;Ru
• Mol File: 14284-93-6.mol

Chemical Properties

• Melting Point: 260 °C (dec.)(lit.)
• Boiling Point: 187.6 °C at 760 mmHg
• Flash Point: 71.9 °C
• Appearance: White/Crystalline
• Vapor Pressure: 0.174mmHg at 25°C
• Storage Temp.: Store below +30°C.
• Water Solubility: Soluble in most organic solvents such as acetone, chlorinated hydrocarbons, alcohols, cyclohexane and benzene. Insoluble in wate
• CAS DataBase Reference: Ruthenium acetylacetonate(CAS DataBase Reference)
• NIST Chemistry Reference: Ruthenium acetylacetonate(14284-93-6)
• EPA Substance Registry System: Ruthenium acetylacetonate(14284-93-6)

Safety Data

• Hazard Codes: Xi,T
• Statements: 36/37/38
• Safety Statements: 26-36-24/25
• WGK Germany: 3
• F: 10
• TSCA: Yes
• Hazardous Substances Data: 14284-93-6(Hazardous Substances Data)

Usage

Uses

Used in Chemical Synthesis:
Ruthenium acetylacetonate is used as a recyclable catalyst for specific organic transformations, such as the acetylation of phenols, alcohols, and amines under neat conditions. Its ability to facilitate these reactions makes it a valuable component in the synthesis of various organic compounds.
Used in Homogeneous Catalysis:
In the field of homogeneous catalysis, Ruthenium acetylacetonate is employed as a catalyst for the hydrolysis of sodium borohydride and the regiospecific tritiation of aromatic carboxylic acids. Its homogeneous nature allows for efficient and selective catalysis in these processes.
Used in Enantioselective Hydrogenation:
Ruthenium acetylacetonate is also used as a catalyst for enantioselective hydrogenation of acids, such as aryl acrylic acid and aryl propenic acid. This application is particularly important in the pharmaceutical and fine chemicals industries, where the production of enantiomerically pure compounds is crucial for the development of effective drugs and other specialty products.
Used in Catalyst Research and Development:
Due to its versatile catalytic properties, Ruthenium acetylacetonate is also used in the research and development of new catalysts and catalytic processes. Its unique characteristics make it an attractive candidate for the design and synthesis of novel catalysts with improved performance and selectivity in various chemical reactions.

Purification Methods

Purify the complex by recrystallisation from *benzene. [Wilkinson J Am Chem Soc 74 6146 1952, Beilstein 1 IV 3677.]

InChI:InChI=1/3C5H8O2.Ru/c3*1-4(6)3-5(2)7;/h3*3,6H,1-2H3;/q;;;+3/p-3/b3*4-3-;

Upstream product

• 26567-75-9 acetylacetone enol 
• 13257-81-3 4-trimethylsiloxy-3-penten-2-one 
• 108-88-3 toluene 
• 870-50-8 di-tert-butyl-diazodicarboxylate 
• 10049-08-8 ruthenium(III)chloride 
• 123-54-6 acetylacetone 
• 14898-67-0 ruthenium trichloride hydrate 
• 31817-84-2 aquachlororuthenium(III) 
• 14898-67-0 ruthenium(III) chloride trihydrate 
• 14898-67-0 ruthenium trichloride hydrate 
• 63767-78-2 ruthenium trichloride 
• 15435-71-9 sodium acetylacetonate 
• 19393-11-4 potassium acetylacetonate 
• 780758-95-4 [Ru(acac)₂(CH₃CN)₂]PF₆ 

Downstream Products

• 111267-19-7 tris(N-p-methoxyphenyl-salicylaldiminato)ruthenium(III) 
• 1287-13-4 bis(η⁵-cyclopentadienyl)ruthenium 
• 21595-26-6 hexachlororuthenate(III)^(3-) 
• 27599-25-3 dihydridotetrakis(triphenylphosphine)ruthenium 
• 117227-79-9 Ru(NPhsal)3 
• 15243-33-1 dodecacarbonyl-triangulo-triruthenium 
• 16406-48-7 ruthenium pentacarbonyl 
• 123-54-6 acetylacetone 
• 7440-18-8 ruthenium 
• 533-75-5 2-hydroxy-2,4,6-cycloheptatrien-1-one 

Relevant articles and documents

A new coordination mode of the photometric reagent glyoxalbis(2- hydroxyanil) (H2gbha): Bis-bidentate bridging by gbha2- in the redox series {(μ-gbha)[Ru(acac)2]2}n (n = -2, -1, 0, +1, +2), including a radical-bridged diruthenium(III) and a RuIII/RuIV intermediate

The bis-bidentate bridging function of gbha2- with N,O -/N,O- coordination was observed for the first time in the complex (μ-gbha)[RuIII(acac)2]2 (1). Density functional theory calculations of 1 yield a triplet ground state with a large (ΔE > 6000 cm-1) singlet-triplet gap. Intermolecular antiferromagnetic coupling was observed (J ≈ -5.3 cm-1) for the solid. Complex 1 undergoes two one-electron reduction and two one-electron oxidation steps; the five redox forms {(μ-gbha)[Ru(acac)2] 2}n (n = -2, -1, 0, +1, +2) were characterized by UV-vis-NIR spectroelectrochemistry (NIR = near infrared). The paramagnetic intermediates were also investigated by electron paramagnetic resonance (EPR) spectroscopy. The monoanion with a comproportionation constant Kc of 2.7 × 108 does not exhibit an NIR band for a Ru III/RuII mixed-valent situation; it is best described as a 1,4-diazabutadiene radical anion containing ligand gbha?3-, which binds two ruthenium(III) centers. A RuIII-type EPR spectrum with g1 = 2.27, g2 = 2.21, and g3 = 1.73 is observed as a result of antiferromagnetic coupling between one RuIII and the ligand radical. The EPR-active monocation (Kc = 1.7 × 106) exhibits a broad (Δν1/2 = 2600 cm -1) intervalence charge-transfer band at 1800 nm, indicating a valence-averaged (Ru3.5)2 formulation (class III) with a tendency toward class II (borderline situation).

Reductive approach to mixed valency (n = 1-) in the Pyrazine Ligand-Bridged [(acac)2Ru(μ-L2-)Ru(acac)2]n (L2- = 2,5-pyrazine-dicarboxylate) through experiment and theory

The diruthenium(III) complex [(acac)2Ru(μ-L 2-)Ru(acac)2] (1) with acac- = acetylacetonato = 2,4-pentanedionato and a 2,5-pyrazine-dicarboxylato bridge, L2-, has been obtained and structurally characterized as the rac (ΔΔ, ΛΛ) diastereomer. The RuIIIRuIII configuration in 1 (dRu-Ru = 6.799 A) results in a triplet ground state (μ = 2.82 μB at 300 K) with a density functional theory (DFT) calculated triplet-singlet gap of 10840 cm-1 and the metal ions as the primary spin-bearing centers (Mulliken spin densities: Ru, 1.711; L, 0.105; acac, 0.184). The paramagnetic 1 exhibits broad, upfield shifted 1H NMR signals with δ values ranging from -10 to -65 ppm and an anisotropic electron paramagnetic resonance (EPR) spectrum (〈g〉 = 2.133, g1 - g3 = Δg = 0.512), accompanied by a weak half-field signal at g = 4.420 in glassy frozen acetonitrile at 4 K. Compound 1 displays two closely spaced oxidation steps to yield labile cations. In contrast, two well separated reversible reduction steps of 1 signify appreciable electrochemical metal-metal interaction in the Ru IIRuIII mixed-valent state 1- (Kc ≈ 107). The intermediate 1- shows a weak, broad Ru II→RuIII intervalence charge transfer (IVCT) band at about 1040 nm (ε = 380 M-1 cm-1); the DFT approach for 1- yielded Mulliken spin densities of 0.460 and 0.685 for the two metal centers. The monitoring of the νC=O frequencies of the uncoordinated C=O groups of L2- in 1n by IR spectroelectrochemistry suggests valence averaging (Ru2.5Ru 2.5) in 1- on the vibrational time scale. The mixed-valent 1- displays a rhombic EPR signal (〈g〉 = 2.239 and Δg = 0.32) which reveals non-negligible contributions from the bridging ligand, reflecting a partial hole-transfer mechanism and being confirmed by the DFT-calculated spin distribution (Mulliken spin density of -0.241 for L in 1-). The major low energy electronic transitions in 1n (n = 0,-,2-) have been assigned as charge transfer processes with the support of TD-DFT analysis.

Study of temperature dependencies of saturated vapor pressure of ruthenium(III) beta-diketonate derivatives

Complexes of ruthenium(III) with the following beta-diketones: 2,4-pentanedione (Ru(acac)3), 1,1,1-trifluoro-2,4-pentanedione (Ru(tfac)3), 2,2,6,6-tetramethyl-3,5-heptanedione (Ru(thd) 3), 2,2,6,6-tetramethyl-4-fluoro-3,5-

Inversion of axial chirality in coordinated bis-β-diketonato ligands

Mononuclear and dinuclear ruthenium(iii) complexes with bis-β-diketonato ligands (denoted by [Ru(acac)2(L-LH)] and [Ru(acac)2(L-L)Ru(acac)2], respectively) were synthesized, where acac, L-LH- and L-L2- denote acetylacetonato, monoprotonated and unprotonated bis-β-diketonato ligands, respectively. The following three ligands were used as the bis-β-diketonato ligand (L-L 2-): 1,2-diacetyl-1,2-dibenzoylethanato (denoted by dabe 2-), 1,2-diacetyl-1,2-bis(3-methylbutanoyl)ethanato (baet 2-) and 1,2-diacetyl-1,2-dipropanoylethanato (dpe2-). For the mononuclear and the meso-type dinuclear complexes, a pair of diastereomeric species were identified as Δ- (or Λ-) [Ru(acac)2(R- or S-L-LH)] and [Δ-Ru(acac)2(R- or S-L-L)Λ-Ru(acac) 2], respectively. The possibility of thermal inversion in coordinated L-LH- (mononuclear) or L-L2- (dinuclear) was pursued by monitoring the changes in the electronic circular dichroism or the 1H NMR spectra. No inversion occurred for the dinuclear complexes, when their chloroform solutions were kept at 50 °C for ca. 100 h. In contrast, some of the mononuclear complexes underwent the inversion of axial chirality to give an equilibrium mixture under the same conditions. The reaction followed the first-order rate law and the overall first-order rate constants (k) of [Ru(acac)2(L-LH)] were determined to be k = 0.13, 0.0048 and less than 0.001 h-1 for L-LH- = dabeH-, baetH - and dpeH-, respectively. The results suggest that the main factor determining the barrier height of the internal rotation is not the steric but the electronic properties of the carbon-carbon bond connecting the two β-diketonato moieties. The Royal Society of Chemistry 2013.

Volatile β-diketonato complexes of ruthenium, palladium and platinum preparation and thermal characterization

Ruthenium, palladium and platinum complexes of 2,2,6,6-tetramethyl-3,5-heptanedione (thd) and ruthenium tris acetylacetonate (acac) were synthetized and studied with TG, DTA, DSC and MS methods. Thermal properties of ruthenocene were also studied. The pla

A NEW METHOD FOR SYNTHESIS OF RUTHENIUM(III) AND RUTHENIUM(II) COMPLEXES OF β-DIKETONES FROM RUTHENIUM BLUE SOLUTION

The blue solution obtained by reducing hydrated ruthenium(III) trichloride with ethanol is used as a convenient starting material in the synthesis of several tris(Β-diketonato)ruthenium(III) and tris(Β-diketonato)ruthenate(II) complexes.The Hammett constans of the substituents on the ligand serve as a helpful guide for choosing the operating conditions.

Kinetics and Mechanisms of Ligand Exchange Reactions of Tris(acetylacetonato)-chromium(III), cobalt(III), ruthenium(III), and -rhodium(III) in Acetylacetone

Tris(acetylacetonato)-cobalt(III), -chromium(III), -ruthenium(III), and -rhodium(III) undergo ligand exchange in acetylacetone(Hacac) at 85-190 deg C without decomposition of the complexes.The exchange rate is proportional to the complex concentration, and the first-order rate constant k0 decreases in the sequence Co(III) above Cr(III) above Ru(III) above Rh(III), k0/10-5 s-1 being 2.4 (93 deg C), 5.6 (117 deg C), 9.5 (158 deg C), and 2.4 (185 deg C), respectively.The activation enthalpies and entropies and deuterium isotope effect on k0 are significantly different between the Co(III) and the Cr(III), Ru(III) and Rh(III) complexes.An intermediate involving an one-ended acetylacetonate and a solvent molecule(Hacac) is concluded to be formed in the rate-determining step.The SN1 and the SN2 mechanism are assigned to the exchange reactions of the Co(III) complex and the others, respectively, for the rate-determining steps.

RUTHENIUM PURE QUADRUPOLE RESONANCE SPECTROSCOPY

The unique chemistry of ruthenium and consequent potential importance of the quadrupole coupling constants and asymmetry parameters of 99Ru and 101Ru has prompted us to initiate an apparently original investigation of the pure nuclear quadrupole resonance spectroscopy of these two isotopes.A means for prediction of the expected resonance frequencies based on Mossbauer data is given and detailed circuit diagrams of a spectrometer which has been constructed primarly for ruthenium studies are presented.Preliminary searches carried out for ruthenium tris-acetylacetonate and bis-ruthenium tetroxide have so far failed to yield signals.Possible explanation for this are discussed and the value of continuing the work defended.

Comparative study of the reactivity of (Cp*RuCl)4 and (Cp*RuCl2)2 with trimethylsilyl-substituted oxodienyl ligands

A comparative study of the chemical reactivity of the well-known precursors [Cp*RuCl]4 (1) and [Cp*RuCl2]2 (2) is established relative to the incorporation of silyl-substituted heterodienyl compounds. This study gives clear evidence of the influence of the solvents and the oxidation state of 1 versus 2 on these reactions. In THF, tetramer 1 reacts selectively with CH2CHCHCHOSiMe3 (3) to afford [Cp*Ru(η4-CH2CHCHCHOSiMe3)Cl] (4), while the reaction of dimer 2 leads to nonselective reactions with the formation of 4 and [Cp*Ruη3-CH2CHCHCHO)Cl2] (5). Compound 5 is thermodynamically more stable than 4. The reactivity of 1 and the mixture of isomers CH2C(Me)CHC(OSiMe3)Me (6a) and MeC(Me)CHC(OSiMe3)CH2 (6b) affords oxo- and pentadienyl compounds [Cp*Ru{η5-CH2C(Me)CHC-(OSiMe 3)CH2}] (7), [Cp*Ru(η5-CH 2C(Me)CHC(Me)O] (8), and [Cp*Ru{η3-exo-syn- CH2C(Me)CHC-(Me)O]Cl2] (9). The treatment of 2 with 3 in methanolic or ethanolic solutions at room temperature provided a preparative route to the corresponding (allyl)ruthenium(IV) species: 5, [Cp*Ru{η3-endo-CH(Me)CHCHOR]Cl2] [R = Me (10); R = Et (12)]; [Cp*Ru{η3-endo-CH2CHCHCH(OR) 2}Cl2] [R = Me (11); R = Et (13)]. The ratio of the species formed could change significatively depending on the ratios of reactants or reaction conditions. The acetal derivatives 10-13 are generated as the result of nucleophilic attack of the alcohols on compound 5. When zinc is used as a reducing agent in ethanol, compound 2 reacts with 3 or the mixture of 6a and 6b to give trimetallic compounds Cp*Ru[η5-CH 2C(R)CHC(R)O]2(μ2-ZnCl2) (R = H, 14; R = Me, 15), which have a ZnCl2 bridging two Cp*Ru[η5-CH2C(R)CHC(R)O] molecules through the oxygen atoms of die corresponding oxopentadienyl ligands, along with [Cp*Ru{η4-CH2C(R)CHC(R)X}Cl] [R = H, X = OEt, 17; R = Me, X = OH, 18] as minor products. 15 reacts in the presence of CDCl3 to give the oxidative addition products exo-syn-9 and [Cp*Ru{η3-endo-anti-CH2C(Me)CHC(Me)O}Cl 2] (19). All compounds have been fully characterized by 1H and 13C NMR spectroscopy, and the crystal structures of 5, 9, 12, and 15 are also described.

Charged, but found not guilty : Innocence of the suspect bridging ligands [RO(O)CNNC(O)OR]2- = L2- in [(acac) 2Ru(μ-L)Ru(acac)2]n, n = +,0,-,2-

Neutral diastereoisomeric diruthenium(III) complexes, meso- and rac-[(acac)2Ru(μ-adc-OR)Ru(acac)2] (acac- = 2,4-pentanedionato and adc-OR2- = dialkylazodicarboxylato = [RO(O)CNNC(O)OR]2-, R = tert-butyl or isopropyl), were obtained from electron transfer reactions between Ru(acac)2(CH3CN) 2 and azodicarboxylic acid dialkyl esters (adc-OR). The meso isomer 3 with R = isopropyl was structurally characterized, revealing two deprotonated and N-N coupled carbamate functions in a reduced dianionic bridge with d N-N = 1.440(5) A. A rather short distance of 4.764 A has been determined between the two oxidized, antiferromagnetically coupled Ru III centers. The rac isomer 4 with R = isopropyl exhibited stronger antiferromagnetic coupling. While the oxidation of the neutral compounds was fully reversible only for 3 and 4, two well-separated (108 c 10) reversible one-electron reduction steps produced monoanionic intermediates 1--4- with intense (ε ≈ 3000 M-1 cm-1), broad (δv1/2 ≈ 3000 cm-1) absorptions in the near-infrared (NIR) region around 2000 nm. The absence of electron paramagnetic resonance (EPR) signals even at 4 K favors the mixed-valent formulation RuII(adc-OR 2-)RuIII with innocently behaving bridging ligands over the radical-bridged alternative RuII(adc-OR?-)Ru II, a view which is supported by the metal-centered spin as calculated by density functional theory (DFT) for the methyl ester model system. The second reduction of the complexes causes the NIR absorption to disappear completely, the EPR silent oxidized forms 3+ and 4+, calculated with asymmetrical spin distribution, do not exhibit near infrared (NIR) activity. The series of azo-bridged diruthenium complex redox systems [(acac)2Ru(μ-adc-R)Ru(acac)2]n (n = +,0,-,2-), [(bpy)2Ru(μ-adc-R)Ru(bpy)2]k (k = 4+,3+,2+,0,2-), and [(acac)2Ru(μ-dih-R)Ru(acac)2] m (m = 2+,+,0,-,2-; dih-R2- = 1,2-diiminoacylhydrazido(2-) ) is being compared in terms of electronic structure and identity of the odd-electron intermediates, revealing the dichotomy of innocent vs noninnocent behavior.