共查询到20条相似文献,搜索用时 15 毫秒
1.
《Journal of organometallic chemistry》1987,331(3):379-385
Dodecacarbonyltriruthenium (Ru3(CO)12) showed high catalytic activity for the first one-to-one addition of N-substituted formamides to both terminal and internal olefins at 180-200°C under a carbon monoxide pressure of 20 kg cm−2. The addition of N-metylformamide to cyclopentene afforded N-methylcyclopentanecarboxamide in 90% yield. 相似文献
2.
《Journal of organometallic chemistry》1986,309(3):333-344
Dodecacarbonyltriruthenium (Ru3(CO)12) is an effective homogeneous catalyst precursor for the carbonylation of amines and hydroamidation of olefins under a carbon monoxide pressure of 40 kg cm−2 at 120–180°C. By the carbonylation of benzylamine, N-benzylformamide was obtained in 77% yield. 1-Octene was hydroamidated with benzylamine to N-benzylnonanamide in 67% yield (the selectivity to its linear isomer was 81%). These reactions appear to include ruthenium carbamoyl complex as the common key intermediate. 相似文献
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Mieock Kim Moon Young Jin Chul Wee Lee Chong Shik Chin 《Journal of organometallic chemistry》2004,689(22):3535-3540
The second generation of Grubbs type catalyst, (PCy3)(H2IMes)Cl2RuCHPh (1) undergoes the Cl replacement with CH3CN to give cationic ruthenium carbene complexes, [(RCN)3(H2IMes)RuCHPh](OTf)2 (2, R = CH3 (a), Ph (b)) in the presence of AgOTf. The reaction of 2a with H2O in the presence of CH3CN gives (aqua)ruthenium complex, [Ru(H2IMes)(NCCH3) 4(H2O)](OTf)2 (3) and benzaldehyde. Benzaldehyde is also observed in the reaction of 1 with H2O. Plausible reaction pathways are suggested for the degradation of ruthenium benzylidenes to give benzaldehyde on the basis of the isotope labeling experiments. 相似文献
5.
Ramanathan Hariram Bidyut Kumar Santra Goutam Kumar Lahiri 《Journal of organometallic chemistry》1997,540(1-2):155-163
The reaction of RuII(PPh3)3X2 (X = Cl, Br) with o-(OH)C6H4C(H)=N-CH2C6H5 (HL) under aerobic conditions affords RuII(L)2(PPh3)2, 1, in which both the ligands (L) are bound to the metal center at the phenolic oxygen (deprotonated) and azomethine nitrogen and RuIII(L1)(L2)(PPh3), 2, in which one L is in bidentate N,O form like in complex 1 and the other ligand is in tridentate C,N,O mode where cyclometallation takes place from the ortho carbon atom (deprotonated) of the benzyl amine fragment. The complex 1 is unstable in solution, and undergoes spontaneous oxidative internal transformation to complex 2. In solid state upon heating, 1 initially converts to 2 quantitatively and further heating causes the rearrangement of complex 2 to the stable RuL3 complex. The presence of symmetry in the diamagnetic, electrically neutral complex 1 is confirmed by 1H and 31P NMR spectroscopy. It exhibits an RuII → L, MLCT transition at 460 nm and a ligand based transition at 340 nm. The complex 1 undergoes quasi-reversible ruthenium(II)—ruthenium(III) oxidation at 1.27V vs. SCE. The one-electron paramagnetic cyclometallated ruthenium(III) complex 2 displays an L → RuIII, LMCT transition at 658 nm. The ligand based transition is observed to take place at 343 nm. The complex 2 shows reversible ruthenium(III)—ruthenium(IV) oxidation at 0.875V and irreversible ruthenium(III)—ruthenium(II) reduction at −0.68V vs. SCE. It exhibits a rhombic EPR spectrum, that has been analysed to furnish values of axial (6560 cm−1) and rhombic (5630 cm−1) distortion parameters as well as the energies of the two expected ligand field transitions (3877 cm−1 and 9540 cm−1) within the t2 shell. One of the transitions has been experimentally observed in the predicted region (9090 cm−1). The first order rate constants at different temperatures and the activation parameter ΔH#/ΔS# values of the conversion process of 1 → 2 have been determined spectrophotometrically in chloroform solution. 相似文献
6.
Alexandr L. Osipov Lyudmila G. Kuzmina Dmitry A. Lemenovskii Georgii I. Nikonov 《Journal of organometallic chemistry》2007,692(22):5081-5085
This paper reports facile preparation of half-sandwich trihydrido complexes of ruthenium based on the reactions of the readily available precursors [Cp(R3P)Ru(NCCH3)2][PF6] with LiAlH4. The target complexes were characterized by spectroscopic methods and X-ray structure analysis of . 相似文献
7.
Prasad S Naik RM Srivastava A 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2008,70(5):958-965
The ruthenium catalyzed oxidation of tris(2-aminoethyl)amine (TREN) by hexacyanoferrate(III) has been utilized for the development of a new and sensitive catalytic kinetic method (CKM) for the determination of ruthenium(III). The reaction was followed spectrophotometrically by the decrease in absorbance at 420nm (lambda(max) of [Fe(CN)(6)](3-)). The CKM developed utilizes fixed time procedure under optimum reaction conditions where the change in absorbance (DeltaA(t)) versus ruthenium(III) concentrations is plotted. The calibration curve recommended for the method is linear in the concentration range 10.11-252.67ngml(-1) with very good accuracy and reproducibility and a maximum error 2.20%. The detection limits of the method for ruthenium(III) corresponding to 10, 15 and 20min are 8.02, 5.03 and 3.15ngml(-1), respectively. The ruthenium(III) has also been determined in the presence of several other interfering and non-interfering cations and anions and no foreign ions interfered in the determination of ruthenium(III) up to five-fold higher concentration of the foreign ions tested. The method is highly sensitive, selective and stable. It has successfully been applied for the determination of trace ruthenium(III) in some synthetic and environmental water samples. A review of most of the published catalytic kinetic and some other important methods for the determination of ruthenium has also been presented. 相似文献
8.
Two-dimensional ruthenium nanoparticles between graphite layers: The effect of reduction temperature
《印度化学会志》2023,100(6):101011
A mixture of graphite powder and ruthenium chloride (III) anhydrous was treated at 723 K under 0.3 MPa chlorine for 3 days, followed by reduction under 40 kPa of hydrogen for 1 h to produce ruthenium metal particles intercalated between graphite layers (Ru-GIC). The structures of ruthenium particles depended on the reduction temperatures. Sheet-like ruthenium particles with 1–3 nm thickness and 10 to several hundred nm width containing numerous irregularly shaped holes with round edge, were formed by reduction at 573 K. A Ru-GIC sample treated at 653 K possessed two-dimensional ruthenium nanosheets with hexagonal holes (straight lines intersect at an angle of 120°) in a similar range of thickness and width. On the other hand, Ru-GIC samples reduced at 773 and 823 K showed two-dimensional plate morphology with a thickness of 1–4 nm. In addition, ruthenium nanoparticles supported on the graphite surface (Ru/Gmix) were also prepared from a slurry of ruthenium chloride (III) hydrate and graphite powder by impregnation and hydrogen reduction. The ruthenium particles in Ru/Gmix were spherical at about 3.6 nm, and the reduction temperature did not affect their particles size. Both Ru-GIC and Ru/Gmix samples were evaluated for cinnamaldehyde (CAL) hydrogenation in supercritical carbon dioxide solvent at 323 K, and they were active to produce cinnamyl alcohol (COL) and hydrocinnamaldehyde (HAL). However, Ru-GIC samples showed higher COL selectivity than Ru/Gmix prepared at the same reduction temperature, and COL selectivity over Ru-GIC increased with the reduction treatments at 773 and 823 K. 相似文献
9.
Matthias Freytag Frank T. Edelmann Ludger Ernst Peter G. Jones Reinhard Schmutzler 《无机化学与普通化学杂志》2004,630(3):377-383
The reaction of the symmetric diphosphene 2, 4, 6‐(CF3)3‐C6H2‐P=P‐C6H2‐2, 4, 6‐(CF3)3 4 with Ru3(CO)12 led to the 50‐electron Ru3P2 nido‐cluster Ru3(CO)9[μ‐P‐C6H2‐2, 4, 6‐(CF3)3]2 5 , which in solution at room temperature displays hindered rotation of the aromatic rings about the C(aryl)—P bonds. The structure of 5 was determined by X‐ray crystal structure analysis; its Ru3P2 centre forms a distorted square pyramid with one ruthenium atom at the apex. One of the two C6H2(CF3)3 groups is also appreciably distorted. Temperature‐dependent 19F NMR studies of the [A3M3X]2 spin system (A = M = CF3, X = 31P) of 5 indicated a rotational barrier ΔG≠ of 82.3 kJ mol‐1 at 141 °C. The same Ru3P2 core was obtained by the reaction of the unsymmetric diphosphene Mes*‐P=P‐Mes 11 with Ru3(CO)12; hindered rotation about the C(aryl)—P bonds was also observed, in this case. 相似文献
10.
Yaohang Cheng Yuhang He Jie Zheng Hui Yang Jun Liu Guanghui An Guangming Li 《中国化学快报》2021,32(4):1437-1441
A Ru(II)-catalyzed para-difluoroalkylation of aromatic aldehydes and ketones with a transient directing group has been developed. It utilizes less expensive ruthenium catalysts and allows facile access to challenging difluoroalkylated aldehydes. The mechanism studies suggest that the distinct coordination mode of ruthenium complex with imine moieties is responsible for para-selectivity. 相似文献
11.
N. d’Alessandro L. Tonucci L.K. Dragani M. Bressan 《Journal of organometallic chemistry》2005,690(8):2133-2141
The thermal and photochemical stabilities were investigated for tetrasulfophthalocyanines of Cu, Co, Ni, Fe and Ru (MPcS) and for two monosulfophthalocyanines of Ru, either without (RuPcS1) or with the coordination of two units of DMSO in apical positions ([RuPcS1(DMSO)2]DMSO). The thermal degradation of all of the studied complexes never showed the formation of spectroscopically detectable intermediates. CuPcS was the most stable complex, while all of the Ru-sulfophthalocyanines were particularly prone to thermal degradation. Photodegradation showed a better selectivity, and as with thermal degradation, the order of reactivity goes from the most stable CuPcS, to the least stable Ru-sulfophthalocyanines (RuPcS, RuPcS1 and [RuPcS(DMSO)2]DMSO). In particular, when the RuPcS complex was irradiated, a stable intermediate was detected that had an absorption band at 532 nm and a mass spectrum attributable to the tetrasulfophthalocyanine from oxidative ring cleavage by the action of the singlet oxygen formed via 1*RuPcS photosensitization. The most probable molecular formula demonstrates a new complex, with a cleaved ring containing an -NO group and two -OH groups that are all bonded at the two extremities of the open-chain molecule. 相似文献
12.
Single crystals of the title compounds were prepared by solid state reactions from barium carbonate and ruthenium metal using a BaBr2 flux and investigated by X-ray diffraction method using Mo(Kα) radiation and a Charge Coupled Device (CCD) detector. A structural model for the term n=2, Ba5Ru2Br2O9 (1) was established in the hexagonal symmetry, space group P63/mmc, a=5.8344(2) Å, c=25.637(2) Å, Z=2. Combined refinement and maximum-entropy method (MEM) unambiguously show the presence of CO32− ions in the three other compounds (2, 3, 4). Their crystal structures were solved and refined in the trigonal symmetry, space group , a=5.8381(1) Å, c=15.3083(6) Å for the term n=3, Ba6Ru3Br1.54(CO3)0.23O12 (2), and space group , a=5.7992(1) Å, c=52.866(2) Å and a=5.7900(1) Å, c=59.819(2) Å for the terms n=4, Ba7Ru4Br1.46(CO3)0.27O15 (3), and n=5, Ba8Ru5Br1.64(CO3)0.18O18 (4), respectively. The structures are formed by the periodic stacking along [0 0 1] of (n+1) hexagonal close-packed [BaO3] layers separated by a double layer of composition [Ba2Br2−2x(CO3)x]. The ruthenium atoms occupy the n octahedral interstices created in the hexagonal perovskite slabs and constitute isolated dimers Ru2O9 of face-shared octahedra (FSO) in 1 and isolated trimers Ru3O12 of FSO in 2. In 3 and 4, the Ru2O9 units are connected by corners either directly (3) or through a slab of isolated RuO6 octahedra (4) to form a bidimensional arrangement of RuO6 octahedra. These four oxybromocarbonates belong to the family of compounds formulated [Ba2Br2−2x(CO3)x][Ban+1RunO3n+3] where n represents the thickness of the octahedral string in hexagonal perovskite slabs. These compounds are compared to the oxychloride series. 相似文献
13.
The reaction of a ruthenium carbide complex RuCl2(C:)(PCy3)2 with [H(Et2O)x]+[BF4]– at a molar ratio of 1:2 produced a two-core ruthenium carbene complex, {[RuCl(=CHPCy3)(PCy3)]2(μ-Cl)3}+·[BF4]–, in the form of a yellow-green crystalline solid in a yield of 94%. This two-core ruthenium complex is a selective catalyst for ring closing metathesis of unsubstituted terminal dienes. More importantly, no isomerized byproduct was observed for N-substrates when the two-core ruthenium complex was used as the catalyst at an elevated temperature(137 °C), indicating that the complex is a chemo-selective catalyst for ring closing metathesis reactions. 相似文献
14.
酸性介质中痕量Ru(Ⅲ)的存在对高碘酸钾氧化偶氯膦pA的褪色反应有明显的催化作用。此文研究了褪色反应的最佳条件,其Ru(Ⅲ)的检出限为5μg.L^-1,钌在5~32μg.L^-1范围内符合比耳定律,由此建立了痕量钌的催化光度分析法,方法可直接在水相中进行,用于贵金属精矿中钌的测定,结果满意。 相似文献
15.
酸性介质中痕量 Ru( )的存在对高碘酸钾氧化偶氮氯膦 p A的褪色反应有明显的催化作用。此文研究了褪色反应的最佳条件 ,其 Ru( )的检出限为 5μg· L-1,钌在 5~ 32μg· L-1范围内符合比耳定律。由此建立了痕量钌的催化光度分析法。方法可直接在水相中进行 ,用于贵金属精矿中钌的测定 ,结果满意 相似文献
16.
RuS4Cl12 and Ru2S6Cl16, Two New Ruthenium(II) Complexes with SCl2 Ligands Ru powder was reacted with SCl2 in closed silika ampoules at 140 °C. From the black solution three compounds RuS4Cl12 1 , Ru2S6Cl16 2 , and Ru2S4Cl13 3 could be crystallized and characterized by x ray analysis. Black crystals of 1 (monoclinic, a = 9.853(1) Å, b = 11.63(1) Å, c = 15.495(1) Å, β = 105.23(1)°, space group P21/c, z = 4) are identified as Trichlorsulfonium‐tris(dichlorsulfan)trichloro‐ruthenat(II) SCl3[RuCl3(SCl2)3]. In the structure the complex anions fac‐[RuCl3(SCl2)3]– and the cations [SCl3]+ are connected to ion pairs by three chlorine bridges. The brown crystals of 2 (triclinic, a = 7.754(2) Å, b = 7.997(2) Å, c = 10.708(2) Å, α = 103.74(3)°, β = 98.44(3)°, γ = 108.58(3)°, space group P‐1, z = 1) contain the binuclear complex Bis‐μ‐chloro‐dichloro‐hexakis(dichlorsulfan)‐diruthenium(II), (SCl2)3ClRu(μ‐Cl)2RuCl(SCl2)3 with two fac‐RuCl3(SCl2)3‐units connected by two chlorine bridges. 3 was identifyed as a known mixed valence Ru(II,III) binuclear complex [Cl2(SCl2)Ru(μ‐Cl)3Ru(SCl2)3]. The vibrational spectra and the thermal behaviour of the compounds are discussed. 相似文献
17.
Gareth R.A. Adair 《Tetrahedron letters》2005,46(47):8233-8235
The oxidation of alcohols has been achieved using Grubbs’ catalyst or a ruthenium p-cymene complex without the presence of an added oxidant. 相似文献
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《Journal of Coordination Chemistry》2012,65(17):2981-2991
[RuCl2(NCCH3)2(cod)], an alternative starting material to [RuCl2(cod)] n for the preparation of ruthenium(II) complexes, has been prepared from the polymer compound and isolated in yields up to 87% using a new work-up procedure. The compound has been obtained as a yellow solid without water of crystallization. The complexes [RuCl2(NCR)2(cod)] spontaneously transform into dimers [Ru2Cl(μ-Cl)3(cod)2(NCR)] (R?=?Me, Ph). 1H NMR kinetic experiments for these transformations evidenced first-order behavior. [RuCl2(NCPh)2(cod)] dimerizes slower by a factor of ten than [RuCl2(NCCH3)2(cod)]. The following activation parameters, ΔH #?=?114?±?3?kJ?mol?1 and ΔS #?=?66?±?9?J?K?1?mol?1 for R?=?CH3CN (ΔG #?=?94?±?5?kJ?mol?1, 298.15?K) and ΔH #?=?122?±?2?kJ?mol?1 and ΔS #?=?75?±?6?J?K?1?mol?1 for R?=?Ph (ΔG #?=?100?±?4?kJ?mol?1, 298.15?K), have been calculated from the first-order rate constants in the temperature range 294–323?K. The kinetic parameters are in agreement with a two-step mechanism with dissociation of acetonitrile as the rate-determining step. The molecular structures of [Ru2Cl(μ-Cl)3(cod)2(NCR)] (R?=?Me, Ph) have been determined by X-ray diffraction. 相似文献
20.
本文提出了一个测定钌的超高灵敏的新方法——离心光度法。摩尔吸光系数ε=1.0(±0.05)×10~7L·mol~(-1)·cm~(-1)。钌含量0.05~0.8μg/25ml呈线性关系。所拟定的方法可用于某些低品位物料中钌的分析。对其超高灵敏的显色反应机理进行了探讨。 相似文献