31378-26-4Relevant articles and documents
Multiple one-electron oxidation and reduction of trinuclear bis(2,4-pentanedionato)ruthenium complexes with substituted diquinoxalino[2,3-a:2′,3′-c]phenazine ligands
Ghumaan, Sandeep,Sarkar, Biprajit,Patil, Mahendra P.,Fiedler, Jan,Sunoj, Raghavan B.,Kaim, Wolfgang,Lahiri, Goutam Kumar
, p. 3409 - 3418 (2007)
The complexes (μ3-L1/L2)[Ru(acac)2]3, acac- = 2,4-pentanedionato, L1 = 2,3,8,9,14,15-hexachlorodiquinoxalino[2,3-a:2′,3′-c]phenazine and L2 = 2,3,8,9,14,15- hexamethyldiquinoxalino[2,3-a:2′,3′-c]phenazine, undergo stepwise one-electron oxidation involving a total of three electrons and stepwise one-electron reduction with three (L2) or four electrons (L1). All reversibly accessible states were characterized by UV-Vis-NIR spectroelectrochemistry. Oxidation leads to mixed-valent intermediates {(μ3-L)[Ru(acac)2]3}+ and {(μ3-L)[Ru(acac)2]3}2+ of which the RuIIIRuIIRuII combinations exhibit higher comproportionation constants Kc than the RuIIIRuIIIRuII states - in contrast to a previous report for the unsubstituted parent systems {(μ3-L3)[Ru(acac)2]3}+/2+, L3 = diquinoxalino[2,3-a:2′,3′-c]phenazine. No conspicuous inter-valence charge transfer absorptions were observed for the mixed-valent intermediates in the visible to near-infrared regions. The monocations and monoanions were characterized by EPR spectroscopy, revealing rhombic ruthenium(III) type signals for the former. Electron addition produces ruthenium(II) complexes of the reduced forms of the ligands L, a high resolution EPR spectrum with 14N and 35,37Cl hyperfine coupling and negligible g anisotropy was found for {(μ3-L1)[Ru(acac)2]3}-. DFT calculations of (μ3-L1)[Ru(acac)2]3 confirm several ligand-centered low-lying unoccupied MOs for reduction and several metal-based high-lying occupied MOs for electron withdrawal, resulting in low-energy metal-to-ligand charge transfer (MLCT) transitions.
Method for synthesizing ruthenium (III) acetylacetonate (by machine translation)
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Paragraph 0011; 0025; 0033; 0035-0040; 0042-0044, (2020/09/10)
A method for synthesizing the ruthenium (III) acetylacetonate, which comprises the following steps of: a, dissolving the hydrated ruthenium trichloride in water, reacting with the base to obtain the ruthenium salt solution; b, reacting the ruthenium salt solution with the acetyl acetonate solution; b, purifying the ruthenium salt solution and the acetyl acetonate solution under heating conditions; and obtaining the total reaction equation of the ruthenium (III) chloride solution and the chloride ion content _AOMARKENCODTX0AO_ 80 - 90% 50 ppm. In the formula, HL is a strong acid of a non-coordinating anion acac is acetyl acetonate. M is Na or K; the content of impurity chloride ions is reduced while the high yield of ruthenium (III) acetylacetonate is guaranteed, the product quality is improved, and industrial production is facilitated. (by machine translation)
The metal complex, a chiral nematic liquid crystal composition and crystal (by machine translation)
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Paragraph 0062; 0063, (2019/03/01)
[Problem] helical twisting power (βM ) Is increased, and, compatibility with a large metal complex of a nematic liquid crystal, chiral nematic liquid crystal composition using the same, and a liquid crystal element. (1) Or formula (2) represented by the formula [a] complex. (1) Or formula (2) in the metal complex represented by formula having chirality, nematic liquid crystal compounds containing chiral nematic liquid crystal compositions. Chiral nematic liquid crystal composition is filled between a pair of liquid crystal element. (R is C1 a-20 straight chain alkyl group or an alkoxy group of straight chain C1 a-20)[Drawing] no (by machine translation)
Organoruthenium compound for chemical vapor deposition raw material and production method for the organoruthenium compound
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Page/Page column 6, (2016/04/20)
The present invention is an organoruthenium compound for a chemical vapor deposition raw material, including dodecacarbonyl triruthenium represented by the following chemical formula, wherein the iron (Fe) concentration is 1 ppm or less. The DCR in the present invention can be produced by obtaining crude DCR by directly carbonylating ruthenium through allowing a ruthenium salt and carbon monoxide to react with each other and by purifying the crude DCR by a sublimation method. In the synthesis step, the concentration of Fe in the obtained crude DCR is preferably set at 10 ppm or less.
Inversion of axial chirality in coordinated bis-β-diketonato ligands
Sato, Hisako,Mori, Yukie,Kitazawa, Takafumi,Yamagishi, Akihiko
, p. 232 - 237 (2013/04/10)
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.
Can a meso-type dinuclear complex be chiral?: Dinuclear β-diketonato Ru(III) complexes
Sato, Hisako,Takase, Ryoichi,Mori, Yukie,Yamagishi, Akihiko
, p. 747 - 751 (2012/02/05)
Dinuclear Ru(III) complexes, [Ru(III)(acac)2(dabe)Ru(III)(acac) 2] (acacH = acetylacetone; dabeH2 = 1, 2-diacetyl-1,2-dibenzoylethane) and [Ru(III)(acac)2(tbet)Ru(III) (acac)2] (tbetH2 = 1,1,2,2-tetrabenzoylethane) were synthesized by reacting [Ru(acac)2(CH3CN) 2]PF6 with dabeH2 and tbetH2 respectively, in toluene. The X-ray structural analysis of a meso-type dinuclear Ru(III) complex, ΔΛ-[Ru(III)(acac)2(dabe)Ru(III)(acac) 2], showed that the bridging part became chiral due to the orthogonal twisting of two non-symmetrical β-diketonato moieties. To confirm this conclusion, the complex was resolved chromatographically to provide a pair of optical antipodes. Such chirality in the bridging part was not generated for [Ru(III)(acac)2(tbet)Ru(III)(acac)2], because the β-diketonato moieties in tbet2- are symmetrical.
Synthesis of ruthenium(iii) and rhodium(iii) tris-acetylacetonates and palladium(ii) bis-ketoiminate using microwave heating
Chimitov,Zherikova,Mikheev,Zharkova,Morozova,Igumenov,Arzhannikov,Tumm
, p. 2236 - 2242 (2013/10/01)
Preparation of ruthenium(iii) and rhodium(iii) tris-acetylacetonates and palladium(ii) bisketoiminate (Pd(i-acac)2) under microwave irradiation using different synthetic conditions, both in the solid-phase and in solution, was studied with precise control of parameters. In the solid-phase systems, the preparation of the target product was hindered. The efficiency of the microwave heating increased when liquid phases of the reagent mixtures were used. For Pd(i-acac)2, the highest yield was achieved under elevated temperature of the process, with the reaction time decreasing to several minutes. A laboratory procedure for the microwave synthesis of ruthenium(iii) and rhodium(iii) tris-acetylacetonates and palladium(ii) bis-ketoiminate in aqueous solutions was developed, which allowed us to obtain them in 85, 55, and 80% yields, respectively. These yields are higher than those reported in the literature, with the process becoming considerably less time consuming and laborious.
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-
Roy, Sayak,Sarkar, Biprajit,Imrich, Hans-Georg,Fiedler, Jan,Zalis, Stanislav,Jimenez-Aparicio, Reyes,Urbanos, Francisco A.,Mobin, Shaikh M.,Lahiri, Goutam Kumar,Kaim, Wolfgang
, p. 9273 - 9281 (2012/11/07)
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.
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
Das, Amit,Scherer, Thomas,Maji, Somnath,Mondal, Tapan Kumar,Mobin, Shaikh M.,Urbanos, Francisco A.,Jimenez-Aparicio, Reyes,Kaim, Wolfgang,Lahiri, Goutam Kumar
, p. 7040 - 7049 (2011/10/11)
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
Morozova,Zherikova,Semyannikov,Trubin,Igumenov
, p. 395 - 399 (2009/12/08)
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-
