Carbon monoxide solubility in ionic liquids: determination, prediction and relevance to hydroformylation

The solubility of carbon monoxide in 37 ionic liquids and in some organic solvents has been determined using high-pressure (13)C NMR spectroscopy; a method for predicting the CO solubility is demonstrated, and it was shown that the rate of the hydroformylation of 5-hexen-2-one does not correlate with the CO solubility, as expected from the determined relative solubility of CO compared to H(2).     

Carbonylation of Alkynyl Epoxides: Synthesis of 5-Hydroxy-2,3-dienoate Esters and 2,3-Dihydrofuran-3-ol Derivatives

The carbonylation of alkynyl oxiranes catalyzed by (MePh(2))(4)Pd in the presence of 20 atm of carbon monoxide in methanol gives methyl 5-hydroxy-2,3-pentadienoates in good yields. When the reaction is performed on alkynyl oxiranemethanol derivatives, 4,5-dihydrofuran-3-ol derivatives are obtained stereoselectively. These products arise from the spontaneous cyclization of a dihydroxyallenyl ester intermediate.     

Direct observation of the kinetically relevant site of CO hydrogenation on supported Ru catalyst at 700 K by time-resolved FT-IR spectroscopy

Time-resolved FT-IR spectra of carbon monoxide hydrogenation over alumina-supported ruthenium particles were recorded on the millisecond time scale at 700 K using pulsed release of CO and a continuous flow of H(2)-N(2) (ratio 0.067 or 0.15, 1 atm total pressure). Adsorbed carbon monoxide was detected along with gas phase products methane (3016 and 1306 cm(-1)), water (1900-1300 cm(-1)), and carbon dioxide (2348 cm(-1)). Aside from adsorbed CO, no other surface species were observed. The rate of formation of methane is 2.5 +/- 0.4 s(-1) and coincides with the rate of carbon dioxide growth (3.4 +/- 0.6 s(-1)), thus indicating that CH(4) and CO(2) originate from a common intermediate. The broad band of adsorbed carbon monoxide has a maximum at 2010 cm(-1) at early times (36 ms) that shifts gradually to 1960 cm(-1) over a period of 3 s as a result of the decreasing surface concentration of CO. Kinetic analysis of the adsorbed carbon monoxide reveals that surface sites absorbing at the high frequency end of the infrared band are temporally linked to gas phase product growth. Specifically, a (linear) CO site at 2026 cm(-1) decays with a rate constant of 2.9 +/- 0.1 s(-1), which coincides with the rise constant of CH(4). This demonstrates that the linear CO site at 2026 cm(-1) is the kinetically most relevant one for the rate-determining CO dissociation step under reaction conditions at 700 K.     

Tunable, light-assisted co-generation of CO and H2 from CO2 and H2O by Re(bipy-tbu)(CO)3Cl and p-Si in non-aqueous medium

The light-assisted co-generation of carbon monoxide and hydrogen from carbon dioxide and water is reported. The combination of a homogeneous CO-evolving electrocatalyst and a heterogeneous H(2)-evolving photoelectrode surface provides for tunability of the H(2)/CO ratio. A total Faradaic efficiency of 102 ± 5% and a H(2)/CO ratio of 2:1 were achieved at a low homogeneous catalyst concentration (0.5 mM) in acetonitrile/water mixtures.     

乙炔/空气预混火焰中CO添加对炭黑生成影响的数值分析(英文)

针对乙炔/空气预混火焰中CO添加对炭黑生成的影响进行了详细的数值模拟.通过对含有不同CO添加量的火焰的模拟结果比较,研究CO添加的温度和化学作用对于炭黑形成的影响.计算结果显示CO添加使炭黑的生成单调下降.炭黑体积分数和成核速率随着温度的升高而增加,到达一个阈值后,再随温度的升高而减少.从炭黑生成的H-萃取角度来看,由于反应OH+CO=CO2+H的向右速率增加,H原子增加以及OH自由基减少,CO添加会激发炭黑生成.从炭黑生成的C-添加机理来看,CO添加减小了C2H2的消耗速率,CO添加也有助于炭黑生成,但CO添加降低了燃料中C2H2的体积分数,使得炭黑表面增长速率降低.     

Biosynthesis of the iron-guanylylpyridinol cofactor of [Fe]-hydrogenase in methanogenic archaea as elucidated by stable-isotope labeling

[Fe]-hydrogenase catalyzes the reversible hydride transfer from H(2) to methenyltetrahydromethanoptherin, which is an intermediate in methane formation from H(2) and CO(2) in methanogenic archaea. The enzyme harbors a unique active site iron-guanylylpyridinol (FeGP) cofactor, in which a low-spin Fe(II) is coordinated by a pyridinol-N, an acyl group, two carbon monoxide, and the sulfur of the enzyme's cysteine. Here, we studied the biosynthesis of the FeGP cofactor by following the incorporation of (13)C and (2)H from labeled precursors into the cofactor in growing methanogenic archaea and by subsequent NMR, matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS), electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR-MS) and IR analysis of the isolated cofactor and reference compounds. The pyridinol moiety of the cofactor was found to be synthesized from three C-1 of acetate, two C-2 of acetate, two C-1 of pyruvate, one carbon from the methyl group of l-methionine, and one carbon directly from CO(2). The metabolic origin of the two CO-ligands was CO(2) rather than C-1 or C-2 of acetate or pyruvate excluding that the two CO are derived from dehydroglycine as has previously been shown for the CO-ligands in [FeFe]-hydrogenases. A formation of CO from CO(2) via direct reduction catalyzed by a nickel-dependent CO dehydrogenase or from formate could also be excluded. When the cells were grown in the presence of (13)CO, the two CO-ligands and the acyl group became (13)C-labeled, indicating either that free CO is an intermediate in their synthesis or that free CO can exchange with these iron-bound ligands. Based on these findings, we propose pathways for how the FeGP cofactor might be synthesized.     

A novel and direct synthesis of indoles via catalytic reductive annulation of nitroaromatics with alkynes

Indoles are produced regioselectively and in moderate yields from the reactions of nitroaromatics with alkynes catalyzed by [CpM(CO)2]2 (1; [(eta 5-C5H5)Fe(CO)2]2; [(eta 5-C5Me5)-Fe(CO)2]2; [(eta 5-C5Me5)Ru(CO)2]2) under carbon monoxide.     

一氧化碳在Ru/Al2O3上吸附态的相互转化和稳定性的研究

本文利用差分红外光谱方法研究了不同预处理条件下,CO在4% Ru/Al₂O₃上的吸附,以及H₂和CO在Ru/Al₂O₃上的共吸附。对CO在Ru上吸附态的红外光谱进行了归属,认为2070cm^-1-2060cm^-1的中频谱带是孪生CO吸附态的对称伸缩振动和线式CO吸附态的伸缩振动相叠合的谱带。讨论了表面碳(C_S)、表面氧(O_S)、表面氢(H_S)对CO吸附态的影响,认为CO在Ru上发生岐化反应形成的表面碳可使Ru=CO键加强,共吸附H₂可使Ru-CO键削弱。表面氧促使形成缺电子的中心,在此中心上生成CO孪生吸附态。CO的孪生吸附是活化吸附过程。     

Binding and photodissociation of CO in iron(II) complexes for application in positron emission tomography (PET) radiolabelling

(R-DAB)FeI(2) complexes containing bidentate diimide ligands (R-DAB = RN=CH-CH=NR; R = (i)Pr, c-C(6)H(11)) have been investigated for their ability to react with carbon monoxide to form iron(II) dicarbonyl complexes, (R-DAB)FeI(2)(CO)(2). Solution IR spectroscopy revealed two νCO stretches between 2000 and 2040 cm(-1) corresponding to a cis-arrangement of the carbonyl ligands around the iron. Photochemical decarbonylation was achieved by UV irradiation (365 nm), which occurred within 5 min as evidenced by solution IR spectroscopy. (c-C(6)H(11)-DAB)FeI(2) has been characterised by X-ray crystallography. Reactions using (11)C-labelled carbon monoxide were investigated and revealed that both (R-DAB)FeI(2) species were not effective as trapping complexes due to the low concentrations of [(11)C]CO used in these experiments. A Fe(TPP)(THF)(x) (TPP = tetraphenylporphyrin) complex was investigated with unlabelled CO and the monocarbonyl adduct Fe(TPP)(THF)CO was formed in situ as identified by IR spectroscopy (νCO = 1966 cm(-1)) yet was stable to CO loss upon UV irradiation. Carbonylation reactions of in situ-generated Fe(TPP)(THF)(x) using [(11)C]CO revealed that 97% of the [(11)C]CO stream could be trapped in one pass of the gas at room temperature and at atmospheric pressure.     

Adsorption and co-adsorption of ethylene and carbon monoxide on silica-supported monodisperse Pt nanoparticles: volumetric adsorption and infrared spectroscopy studies

The adsorption of carbon monoxide and ethylene, and their sequential adsorption, was studied over a series of Pt/SBA-15 catalysts with monodisperse particle sizes ranging from 1.7 to 7.1 nm by diffuse-reflectance infrared spectroscopy and chemisorption. Gas adsorption was dependent on the Pt particle size, temperature, and sequence of gas exposure. Adsorption of CO at room temperature on Pt/SBA-15 gives rise to a spectroscopic feature assigned to the C-O stretch: nu(CO) = 2075 cm-1 (1.9 nm); 2079 cm-1 (2.9 nm); 2082 cm-1 (3.6 nm); and 2090 cm-1 (7.1 nm). The intensity of the signal decreased in a sigmoidal fashion with increasing temperature, thereby providing semiquantitative surface coverage information. Adsorption of ethylene on Pt/SBA-15 gave rise to spectroscopic features at approximately 1340, approximately 1420, and approximately 1500 cm-1 assigned to ethylidyne, di-sigma-bonded ethylene, and pi-bonded ethylene, respectively. The ratio of these surface species is highly dependent on the Pt particle size. At room temperature, Pt particles stabilize ethylidyne as well as di-sigma- and pi-bonded ethylene; however, ethylidyne predominated on the surfaces of larger particles. Ethylidyne was the only identifiable species at 403 K, with its formation being more facile on larger particles. Co-adsorption experiments reveal that the composition of the surface layer is dependent on the order of exposure to gases. Exposure of a C2H4-covered Pt surface to CO resulted in an approximately 50% decrease in chemisorbed CO compared to a fresh Pt surface. The nu(CO) appeared at 2050 cm-1 on Pt/SBA-15 pretreated with C2H4 at room temperature. The di-sigma-bonded and pi-bonded species are the most susceptible to displacement from the surface by CO. The formation of ethylidyne appeared to be less sensitive to the presence of adsorbed carbon monoxide, especially on larger particles. Upon exposure of C2H4 to a CO-covered Pt surface, little irreversible uptake occurred due to nearly 100% site blocking. These results demonstrate that carbon monoxide competes directly with ethylene for surface sites, which will have direct implications on the poisoning of the heterogeneously catalyzed conversion of hydrocarbons.     

Modeling of microreactor for syngas production by catalytic partial oxidation of methane

Fixed-bed reactors for the catalytic partial oxidation of methane (CPOM) to produce synthesis gas still pose hot spots problems. Microreactor is a good alternative reactor proposed to resolve these problems. In this paper, synthesis gas (hydrogen and carbon monoxide) production was investigated by a two-dimensional numerical model of single microchannel. CFD modeling with detailed chemistry was conducted to understand the CPOM on platinum (Pt) catalyst. Gas inlet velocity, microchannel pressure, and fuel to air ratio (F/A) are selected as the effective parameters on microchannel performance. Study results show that Reynolds number has considerable effect on methane conversion, hydrogen to carbon monoxide ratio (H2/CO), and product distribution. Increasing gas inlet velocity causes all the above parameters to decrease. It is noted that increasing microchannel pressure and decreasing the ratio of fuel to air cause the decrease of the H2/CO ratio.     

Comparative study of the hydrogen-bonded complexes of phenol and o-cyanophenol with CO Ab initio and DFT approachs

The structures, stability and vibrational spectra of the hydrogen-bonded complexes of carbon monoxide (CO) with phenol and o-cyanophenol (syn and anti) have been studied using ab initio and DFT calculations. Full geometry optimization has been performed for the studied complexes by DFT (BLYP/6-311++G(d,p)) calculations. The calculations show that the hydrogen-bond formation of carbon monoxide (CO) with phenol and o-cyanophenol (syn and anti) leads to the following stable structures: C6H5OH...CO (1A); C6H5OH...OC (1B); (syn) o-CNC6H4OH...CO (2A-syn); (syn) o-CNC6H4OH...OC (2B-syn); (anti) o-CNC6H4 OH...CO (2A-anti) and (anti) o-CNC6H4OH...OC (2B-anti). Having in mind the corrected values of the dissociation energy, the studied hydrogen-bonded complexes can be ordered according their stability as follows: 2A-anti>2A-syn>1A>2B-anti>1B>2B-syn. The predicted red-shifts for the nuOH vibration with the B3LYP/6-311++G(d,p) calculations for the structures 1A (-46 cm-1), 2A-syn (-60 cm-1) and 2A-anti (-73 cm-1) are in very good agreement with the experimentally observed. The magnitudes of the wavenumber shifts are indicative of relatively weak OH...C hydrogen-bonded interactions. The calculations predict an increase of the IR intensity of the nuOH vibration in the complexes 1A, 2A-anti and 2A-syn up to five times.     

碳化钼催化材料的制备、表征及CO加氢反应性能的研究

以MoO3为前驱体,CH4/4H2为碳化介质,通过程序升温反应法(TPRe)制备了不同晶型碳化钼 (β-Mo2C和α-MoC1-x) 催化材料,并通过XRD、BET、TEM、SEM和XPS等表征手段对碳化钼材料的晶体结构、比表面积、形貌及电子特征进行了研究;同时考察了不同晶型碳化钼的CO加氢反应性能。结果表明,其具有很高CO加氢活性,产物主要为烷烃,同时有少量低碳醇生成。因此,碳化钼有望成为新型F T合成或低碳醇合成的催化剂。     

一些含Fe-Sn-Fe键金属有机化合物的穆斯堡尔谱研究

研究了[(π-C5H5)Fe(CO)2]2Sn(X)(Y)类型化合物的穆斯堡尔谱, 表明Fe的参数基本不受X、Y基团性质的影响, 而不同X、Y改变Sn上s电子密度从而引起Sn的参数有规则的变化; X, Y基团的作用性质表明Fe-Sn之间不存在π相互作用.     

Decomposition of neutral, singly and doubly protonated benzoquinone in the gas phase

The unimolecular fragmentations of singly and doubly protonated ortho-, meta-, and para-benzoquinones (BQH(+) and BQH(2)(2+), respectively) are studied by tandem mass spectrometry. The dominant fragmentation pathways lead to the elimination of a neutral CO molecule from BQH(+) and, by charge separation, to the expulsion of protonated CO from BQH(2)(2+). Reaction mechanisms are elucidated based on labeling experiments and UB3 LYP calculations. These results reveal that the respective reactions proceed in an analogous fashion to the decarbonylation of neutral benzoquinones, which decompose into carbon monoxide and cyclopentadienone. Single protonation facilitates all steps on the reaction pathway with neutral CO and O-protonated cyclopentadienone as final products. In contrast, double protonation leads to an increase of the barriers for the decomposition yielding CO.H(+) and O-protonated cyclopentadienone. This major process of BQH(2)(2+) is accompanied by two minor channels, which lead to the elimination of neutral carbon monoxide and water, respectively. The proton affinity of the para-BQH(+) monocation is estimated as 3.6+/-0.3 eV.     

Promoter effect on the CO_2-H_2O formation during Fischer-Tropsch synthesis on iron-based catalysts

The effects of Mg,La and Ca promoters on primary and secondary CO2 and H2O formation pathways during Fischer-Tropsch synthesis on precipitated Fe/Cu/SiO2 catalysts are investigated.The chemisorbed oxygen atoms in the primary pathway formed in the CO dissociation steps reacted with co-adsorbed hydrogen or carbon monoxide to produce H2O and CO2,respectively.The secondary pathway was the water-gas shift reaction.The results indicated that the CO2 production led to an increase in both primary and secondary pathways,and H2O production decreased when surface basicity of the catalyst increased in the order Ca Mg La.     

Electron counting and bonding analysis in triruthenium clusters containing sulfoximido ligands: true or false electron-deficient systems?

Triruthenium clusters containing a methylphenylsulfoximido cap or bridge, Ru₃(CO)₉(μ₂-H)[μ₃-NS(O)MePh] (1), Ru₃(CO)₁₀(μ₂-H)[μ₃-NS(O)MePh] (2), Ru₃(CO)₈(μ₃-η²-CPhCHBu)[μ₃-NS(O)MePh] (3), Ru₃(CO)₉(μ₃-η²-PhCCCCHPh)[μ₂-NS(O)MePh] (4), and Ru₃(CO)₇(μ₂-CO)(μ₃-η²-PhCCCCHPh)[μ₃-NS(O)MePh] (5) have been examined by EHT and DFT calculations in order to analyze the bonding present in the clusters and to establish the electron counting. They clearly show that a μ₃-sulfoximido group is not a 3e⁻ ligand as one may be led to think at first sight, but rather acts as a three-orbital/5e⁻ system, i.e. should be considered as isolobal to an N---R⁻ ligand. Because of some delocalization of its π-type orbitals on the sulfur and oxygen atoms, it is expected to bind slightly less strongly to metal atoms than classical imido ligands. Once in a μ₂ coordination mode, the sulfoximido ligand retains a lone pair on its pyramidalized N atom and becomes a two-orbital/3e⁻ ligand. It follows that clusters 1, 2, 4 and 5 are electron-precise, whereas cluster 3 is electron deficient with respect to the 18e⁻ rule but obeys the polyhedral skeletal electron pair electron-counting rules. Consistently, all the calculated clusters exhibit large HOMO–LUMO gaps and no trace of electron deficiency can be found in their electronic structures.     

Analysis of trace amounts of carbon dioxide, oxygen and carbon monoxide in nitrogen using dual capillary columns and a pulsed discharge helium ionisation detector

Gas mixtures of trace amounts of carbon dioxide (CO(2)), dioxygen (O(2)), and carbon monoxide (CO) in dinitrogen (N(2)) were separated and quantified using parallel dual capillary columns and pulsed discharge helium ionisation detection (PDHID). The detection limits (9 x 10(-9) mol mol(-1) for CO(2), 7 x 10(-9) mol mol(-1) for O(2) and 37 x 10(-9) mol mol(-1) for CO) were lower than those reported previously for similar methods. Uncertainties were calculated and results were validated by comparison of the CO and CO(2) results with those obtained using conventional methods. The method was also used to analyse nitrogen, carbon dioxide and carbon monoxide in oxygen.     

SO2F2‐Mediated One‐Pot Synthesis of Aryl Carboxylic Acids and Esters from Phenols through a Pd‐Catalyzed Insertion of Carbon Monoxide

A one‐pot Pd‐catalyzed carbonylation of phenols into their corresponding aryl carboxylic acids and esters through the insertion of carbon monoxide has been developed. This procedure offers a direct synthesis of aryl carboxylic acids and esters from inexpensive and abundant starting materials (phenols, SO₂F₂ and CO) under mild conditions. This method tolerates a broad range of functional groups and is also applicable for the modification of complicated natural products.