Microwave Irradiation for the Facile Synthesis of Transition‐Metal Nanoparticles (NPs) in Ionic Liquids (ILs) from Metal–Carbonyl Precursors and Ru‐, Rh‐, and Ir‐NP/IL Dispersions as Biphasic Liquid–Liquid Hydrogenation Nanocatalysts for Cyclohexene

Stable chromium, molybdenum, tungsten, manganese, rhenium, ruthenium, osmium, cobalt, rhodium, and iridium metal nanoparticles (M‐NPs) have been reproducibly obtained by facile, rapid (3 min), and energy‐saving 10 W microwave irradiation (MWI) under an argon atmosphere from their metal–carbonyl precursors [M_x(CO)_y] in the ionic liquid (IL) 1‐butyl‐3‐methylimidazolium tetrafluoroborate ([BMIm][BF₄]). This MWI synthesis is compared to UV‐photolytic (1000 W, 15 min) or conventional thermal decomposition (180–250 °C, 6–12 h) of [M_x(CO)_y] in ILs. The MWI‐obtained nanoparticles have a very small (<5 nm) and uniform size and are prepared without any additional stabilizers or capping molecules as long‐term stable M‐NP/IL dispersions (characterization by transmission electron microscopy (TEM), transmission electron diffraction (TED), and dynamic light scattering (DLS)). The ruthenium, rhodium, or iridium nanoparticle/IL dispersions are highly active and easily recyclable catalysts for the biphasic liquid–liquid hydrogenation of cyclohexene to cyclohexane with activities of up to 522 (mol product) (mol Ru)^?1 h^?1 and 884 (mol product) (mol Rh)^?1 h^?1 and give almost quantitative conversion within 2 h at 10 bar H₂ and 90 °C. Catalyst poisoning experiments with CS₂ (0.05 equiv per Ru) suggest a heterogeneous surface catalysis of Ru‐NPs.     

Hydrolysis of ZrF 6 2− anions in solutions of copper(II) ammine and synthesis of Cu x Zr(OH) y F z nanolayers by the ionic layering method

The possibility to synthesize M_1x M₂(OH) _y F _z nanolayers by the ionic layering method with the use of soluble anionic complexes of metal fluorides was demonstrated. The influence of the concentration and pH of reagent solutions and of the number of ionic layering cycles on the kinetics of layer growth was studied using the example of Cu _x Zr(OH) _y F _z layers. The composition of the synthesized layers was studied by X-ray photoelectron (XPE) spectroscopy, ellipsometry, and electronic and Fourier transform IR (FT-IR) transmission spectroscopy.     

Ionic Liquids with More than One Metal: Optical and Electrochemical Properties versus d-Block Metal Combinations

Thirteen N-butylpyridinium salts, including three monometallic [C₄Py]₂[MCl₄], nine bimetallic [C₄Py]₂[M_1−x^aM_x^bCl₄] and one trimetallic compound [C₄Py]₂[M_1−y-z^aM_y^bM_z^cCl₄] (M=Co, Cu, Mn; x=0.25, 0.50 or 0.75 and y=z=0.33), were synthesized and their structure and thermal and electrochemical properties were studied. All compounds are ionic liquids (ILs) with melting points between 69 and 93 °C. X-ray diffraction proves that all ILs are isostructural. The conductivity at room temperature is between 10⁻⁴ and 10⁻⁸ S cm⁻¹. Some Cu-based ILs reach conductivities of 10⁻² S cm⁻¹, which is, however, probably due to IL dec. This correlates with the optical bandgap measurements indicating the formation of large bandgap semiconductors. At elevated temperatures approaching the melting points, the conductivities reach up to 1.47×10⁻¹ S cm⁻¹ at 70 °C. The electrochemical stability windows of the ILs are between 2.5 and 3.0 V.     

Studies on the synergetic effect of group viii transition metal carbonyls on homogeneous catalysis of the water-gas shift reaction

Homogeneous catalysis of the water-gas shift reaction by Group VIII mixed metal carbonyls and by mixtures of Group VIII metal carbonyls in pyridine solution was examined under mild conditions (T= 100°C, P_co = 0.42–0.60 atm).A weak synergetic effect of Group VIII metals was observed between iron and iridium carbonyls. A stronger synergetic behaviour of mixed metal Fe/Ru catalyst precursors (Fe₂Ru(CO)₁₂ and FeRu₂(CO)₁₂) was noted. The effect of phosphine and phosphite substitution on Fe₂Ru(CO)₁₂ and FeRu₂(CO)₁₂ was examined. Only monosubstitution on Fe₂Ru(CO)₁₂ was found to have an enhancing effect on catalytic activity.Rhodium carbonyls, which were found to produce the most active catalyst solution under homogeneous water-gas shift conditions, did not show a synergetic behaviour with other Group VIII metals.     

碱土金属掺杂对钴基尖晶石复合金属氧化物催化分解N_2O性能的影响

采用共沉淀法制备碱土金属掺杂的钴基尖晶石型复合金属氧化物M_xCo_(3-x)O_4(M=Mg、Ca、Sr、Ba;x=0、0.1、0.3、0.5、0.7、0.9)催化剂,使用XRD、SEM、氮吸附、H_2-TPR、O_2-TPD-M S和XPS等技术对催化剂进行表征,并在固定床微型反应器中评价了M_xCo_(3-x)O_4催化剂催化分解N_2O的活性,研究了碱土金属掺杂对其催化性能的影响。结果表明,碱土金属掺杂后,M_(x )Co_(3-x)O_4催化剂颗粒粒径减小,比表面积增大,表面吸附氧和Co~(2+)数量增加,氧化还原性能增强;在反应气组成为0.68%N_2O,3%O_2,Ar为平衡气的条件下,碱土金属锶掺杂、掺杂量x为0.7时,Sr_(0.7)Co_(2.3)O_4的N_2O分解催化活性最高,N_2O转化率为10%和95%时所需的温度分别为312和451℃。     

Model Studies on the Ozone-Mediated Synthesis of Cobalt Oxide Nanoparticles from Dicobalt Octacarbonyl in Ionic Liquids

Low-temperature synthesis in ionic liquids (ILs) offers an efficient route for the preparation of metal oxide nanomaterials with tailor-made properties in a water-free environment. In this work, we investigated the role of 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide [C₄C₁Pyr][NTf₂] in the synthesis of cobalt oxide nanoparticles from the molecular precursor Co₂(CO)₈ with ozone. We performed a model study in ultra-clean, ultrahigh vacuum (UHV) conditions by infrared reflection absorption spectroscopy (IRAS) using Au(111) as a substrate. Exposure of the pure precursor to ozone at low temperatures results in the oxidation of the first layers, leading to the formation of a disordered Co_xO_y passivation layer. Similar protection to ozone is also achieved by deposition of an IL layer onto a precursor film prior to ozone exposure. With increasing temperature, the IL gets permeable for ozone and a cobalt oxide film forms at the IL/precursor interface. We show that the interaction with the IL mediates the oxidation and leads to a more densely packed Co_xO_y film compared to a direct oxidation of the precursor.     

A comparative study on the thermal decomposition of some transition metal carboxylates

Thermal decomposition of transition metal malonates, MCH₂C₂O₄?xH₂O and transition metal succinates, M(CH₂)₂C₂O₄?xH₂O (M=Mn, Fe, Co, Ni, Cu, Zn) has been studied employing TG, DTG, DTA, XRD, SEM, IR and Mössbauer spectroscopic techniques. After dehydration, the anhydrous metal malonates and succinates decompose directly to their respective metal oxides in the temperature ranges 310–400 and 400–525°C, respectively. The oxides obtained have been found to be nanosized. The thermal stability of succinates have been found to be higher than that of the respective malonates.     

Fluorous ionic liquids as solvents for the liquid-liquid extraction of metal ions by macrocyclic polyethers

The predominant mode of strontium ion transfer from aqueous nitrate media into a series of 1-fluoroalkyl-3-methylimidazolium bis[(trifluoromethylsulfonyl)]imides containing dicyclohexano-18-crown-6 (DCH18C6) is shown to shift from cation exchange to strontium nitrato-crown ether complex partitioning as the length of the fluoroalkyl substituent is increased. Fluoroalkyl substituents are shown to be only slightly more effective than their non-fluorous analogs at inducing this shift. At the same time, the fluorinated ionic liquids (ILs) yield strontium distribution ratios as much as an order of magnitude lower than the corresponding 1-alkyl-3-methylimidazolium (C_nmim⁺) salts. Fluorous ILs thus appear to offer no compelling advantages over C_nmim⁺ ionic liquids as extraction solvents.     

Silicate coatings on titanium, modified with transition metal oxides and their activity in CO oxidation

CuO+M _x O _y /TiO₂+SiO₂/Ti composites (M = Mn, Fe, Co, Ni) were produced by plasma-electrolytic oxidation and impregnation, followed by annealing. The elemental and phase composition of these composites were examined and their activity series in CO oxidation was determined.     

Synthesis,infrared spectra and thermoanalytical properties of transition metal sulfite hydrazine hydrates

Transition metal sulfite hydrazine hydrates, MSO₃·xN₂H₄·yH₂O whereM=Mn, Fe, Co, Ni and Zn have been prepared and characterized by chemical analysis, infrared spectra, thermoanalytical and combustion studies. The colours,x andy parameters of the complexes varied depending upon the preparation conditions. Thermal decomposition characteristics differ from metal to metal yielding metal oxides at relatively low temperatures.

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Zusammenfassung Mittels chemischer Analyse, IR-Spektren, thermoanalytischen und Verbrennungsstudien wurden die Hydrazinhydrate der hergestellten Übergangsmetallsulfite MSO₃·xN₂H₄·yH₂O mitM=Mn, Fe, Co, Ni und Zn beschrieben. Farbe sowie die Parameterx undy der Komplexe hängen von den Herstellungsbedingungen ab. Die thermische Zersetzung, bei der bei relativ niedrigen Temperaturen Metalloxide entstehen, ist von Metall zu Metall verschieden.

     

Transition metal oxide clusters with character of oxygen-centered radical: a DFT study

Density functional theory (DFT) calculations are applied to study the structure and bonding properties of groups 3–7 transition metal oxide clusters M _x=1–3O _y ^q and Sc _x=4–6O _y ^q with 2y ? nx + q = 1, in which n is the number of metal valence electrons and q is the charge number. These clusters include MO₂, M ₂O₃ ⁺, M ₂O₄ ^?, and M ₃O₅ (M = Sc, Y, La); MO₂ ⁺, MO₃ ^?, M ₂O₄ ⁺, M ₂O₅ ^?, M ₃O₆ ⁺, and M ₃O₇ ^? (M = Ti, Zr, Hf), and so on. The obtained lowest energy structures of most of these clusters are with character of oxygen-centered radical (O^·). That is, the clusters contain oxygen atom(s) with the unpaired electron being localized on the 2p orbital(s). Chromium and manganese oxide clusters (except CrO₄ ^?) do not contain O^· with the adopted DFT methods. The binding energies of the radical oxygen with the clusters are also calculated. The DFT results are supported by available experimental investigations and predict that a lot of other transition metal oxide clusters including those with mixed-metals (such as TiVO₅ and CrVO₆) may have high oxidative reactivity that has not been experimentally identified. The chemical structures of radical oxygen over V₂O₅/SiO₂ and MoO₃/SiO₂ catalysts are suggested and the balance between high reactivity and low concentration of the radical oxygen in condensed phase catalysis is discussed.     

The synthesis of Fe-containing ionic liquid and its catalytic performance for the dehydration of fructose

Four Fe-containing ionic liquids (ILs) were synthesized by coupling of conventional imidazole ionic liquids [C_xmim]Cl (x = 4, 8, 12, 16) with FeCl₃ and were characterized by FT-IR, Raman, ESI–MS and TG. All of the Fe-containing ILs were applied to the conversion of fructose into 5-hydroxymethylfurfural (HMF) in 1-butyl-3-methylimidazolium chloride ([Bmim]Cl) subsequently and the result showed that [C₁₆mim]FeCl₄ exhibited excellent catalytic performance. Then the different reaction parameters with [C₁₆mim]FeCl₄ as catalyst were studied in detail. A 92.8% yield of HMF was obtained with 0.03 g [C₁₆mim]FeCl₄ and 0.1 g fructose in 1.0050 g [Bmim]Cl at 80 °C for 40 min in fructose/[Bmim]Cl solution.     

Ethylene glycol‐based ionic liquids via azide/alkyne click chemistry

A facile synthetic route for the preparation of dicationic ethylene glycol based‐ionic liquids (ILs) via the azide/alkyne “click” reaction is presented. The copper(I) catalyzed, microwave‐assisted azide/alkyne “click” reaction between diazido‐ethylene glycols and the corresponding alkyne containing IL‐head group enables a simple preparation of different sets of poly(ethylene glycol)‐based ILs. Beside tetra‐ and hexa(ethylene glycol)‐based ILs, also oligomeric (M_n = 400 g/mol) and polymeric ILs (M_n up to 1550 g/mol) could be prepared in good yield and with full conversion of the ionic head group. The prepared ILs were extensively characterized via NMR spectroscopy and ESI‐time‐of‐flight (TOF) mass spectroscopy, revealing the formation of multiply charged ions in the negative mode. Thermal stability proved to be exceptionally high (up to 300 °C) together with low glass‐transition temperatures. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Structural studies of Rh4(CO)12 derivatives in solution and in the solid state

The crystal structures of Rh₄(CO)₁₀(PPh₃)₂ and Rh₄(CO)₉P(OPh)₃₃ are reported. ³¹P-¹H NMR studies on Rh₄(CO)₁₂-_x {P(OPh)₃}_x(X  1, 2 and 3) show that each derivative exists as only one isomer in solution whereas the analogous triphenylphosphine derivatives can exist as different isomers. A quantitative redistribution of triphenylphosphites occurs on mixing Rh_4-(CO)₁₂-_xL_x with Rh₄(CO)₁₂-_yL_y (L  P(OPh)₃; x  0, 1, 2, y  x + 2; x  0, y  x + 4) to give Rh₄(CO)₁₂-_zL_z[z $\text{1}\text{2}$(x + y)]; a related rapid intermolecular randomisation of carbonyls occurs on mixing Rh₄(¹²CO)₁₂ with Rh₄(¹³CO)₁₂.     

Perturbation of metal—metal stretching frequencies by the interaction of lewis acids with bridging carbonyls

Adduct formation on the oxygen of a bridging carbonyl causes a very small perturbation of metal—metal stretching frequencies of polynuclear carbonyls. This small shift contrasts with the large change in v(MM) when carbonyl groups are redistributed between terminal and bridging positions; therefore, using low frequency Raman spectroscopy, it is possible to infer the structural relation of C- and O-bonded adduct to the parent carbonyl. Structural inferences for Fe₃(CO)₁₂ · AlBr₃, Ru₃(CO)₁₂ · AlBr₃ and Fe₂(CO)₉ · AlBr₃ are given.     

Matrix isolated metal carbonyl anions

Cocondensation at 20K of sodium atoms with transition metal carbonyls (e.g. Cr(CO)₆) diluted in argon gives IR spectroscopic evidence for carbonyl anions (e.g. Cr(CO)₅⁻).     

Photoabsorption spectra ofs 1-electron metal clusters

Collinear laser/molecular beam photodepletion spectroscopy has developed into a powerful tool for the determination of electronic absorption in neutral alkali metal clusters free of perturbing matrix effects. We briefly discuss the method, present data on selected Na _x and Li _y Na _x?y ,x≤20, contrast measurements with the known optical response of larger colloidal metal clusters, compare microcluster spectra with the predictions of various models and speculate on future experimental and theoretical developments in this field.     

Experimental Study of the Thermal Decomposition Properties of Binary Imidazole Ionic Liquid Mixtures

Ionic liquids (ILs) have a wide range of applications, owing to their negligible vapor pressure, high electrical conductivity, and low melting point. However, the thermal hazards of ILs and their mixtures are also non-negligible. In this study, the thermal hazards of various binary imidazolium ionic liquids (BIIL) mixtures were investigated. The effects of parent salt components and molar ratios on the thermal decomposition temperature (T_d) and flashpoint temperature (T_f) are investigated. It is found that both T_d and T_f increase as the proportion of highly thermally stable components in BIIL mixtures increases. Furthermore, the decomposition process of BIIL mixtures can be divided into two stages. For most molar ratios, the T_f of the BIIL mixtures is in the first stage of thermal decomposition. When the proportion of highly thermally stable components is relatively high, T_f is in the second stage of thermal decomposition. The flammability is attributed to the produced combustible gases during the thermal decomposition process. This work would be reasonably expected to provide some guidance for the safety design and application of IL mixtures for engineering.     

Reactivity of main-group—transition-metal bonds : VI. the kinetics of iodination of tetracarbonyl(trimethylstannyl)cobalt and pentacarbonyl(trimethylstannyl)rhenium

The kinetics of the iodine cleavage of the SnCo bond in [Me₃SnCo(CO)₄ ] and of the SnRe bond in [Me₃SnRe(CO)₅] have been measured. The order of rates of cleavage of the SnM bond in the compounds [Me₃SnM(CO)_x(cp)_y] (M = Mn, Re, x = 5, y = 0;M = Co, x = 4, y = 0; M = Cr, Mo, W, x = 3, y = 1; M = Fe, x = 2, y = 1; cp = η-cyclopentadienyl) indicates that the main factors determining reactivity towards iodine are the size of the metal atom (M) and the shielding of it by the other ligands.     

Formation of mixed Fe-Mo oxo clusters in the gas phase

Reactions of oxygen-containing molybdenum clusters Mo_xO_y (x = 1–3, y = 1–9) with iron carbonyl ions Fe(CO) _n ⁺ (n = 1–3) were studied by the ion cyclotron resonance technique. The reactions were found to yield mixed Fe-Mo oxo clusters Mo_xO_yFe⁺ (x = 2, 3; y = 5, 6, 8, 9).