Homogeneous catalysis by ruthenium carbonyl clusters

The historical background of and the incentive for using ruthenium carbonyl clusters as homogeneous catalysts are outlined. Keeping in view the possible solutions the uncertainties arising from declusterification and metal colloid formation are discussed. All ruthenium cluster-catalysed reactions are broadly classified as reactions with or without carbon monoxide as one of the reactants and the basic differences between such reactions are highlighted. Some of the factors of special relevance to cluster-catalysed reaction systems are mentioned. The reactions involving carbon monoxide are then discussed. These include water-gas-shift reaction, carbon monoxide hydrogenation, hydroformylation, reductive carbonylation of nitrobenzene and other carbonylation reactions. Hydrogenation, transfer hydrogenation, isomerisation and a few other reactions are then discussed. For all these reactions, special emphasis is laid on well-characterised cluster complexes that have been proposed as catalytic intermediates. Finally an attempt has been made to identify the path that future research in cluster catalysis is likely to follow.     

Metal cluster catalysis. 2. Selective reduction of nitrobenzene catalyzed by rhodium carbonyl cluster anions. Evidence for water gas shift reaction

The rhodium cluster complex, Rh₆(CO)₁₆, has been found to catalyze the homogeneous reduction of nitrobenzene to aniline at temperatures above 80 °C in the presence of N,N-dimenthylbenzylamine, using any one of the following reducing gases: (1) H₂/CO, (2) H₂, (3)CO/H₂O. The reductions are highly selective and aniline was the only product detected. The same result was obtained using Amberlyst A-21 resin beads which contained polymerbound N,N-dimethylbenzylamine moieties which, in turn, immobilize the rhodium clusters. It was shown, by using D₂O, and following deuterium incorporation into the resulting aniline, that the water is the source of hydrogen when CO/H₂O was used. When nitrobenzene is absent, this catalyst system promotes the water—gas shift reaction. Unlike aromatic nitro groups, aliphatic nitro groups were not reduced. However, the water—gas shift reaction was catalyzed. The kinetics of aniline formation were first order in nitrobenzene and the effect of pressure on the reaction is described. Use of the resin catalyst led to lower rates and a remarkably air sensitive catalyst system relative to the homogeneous reactions.     

Catalytic activity of aluminium-rich hematite in the water gas shift reaction

Aluminium-rich hematite was found to catalyze the water gas shift reaction but there is a compromise between the increase in specific surface area and the intrinsic activity. This revised version was published online in June 2006 with corrections to the Cover Date.     

Organosilicon chemistry : XXX. Homogeneous catalysis by iridium(I) complexes of the reaction between silanes and alcohols or dideuterium

The complexes IrX(CO)L₂, IrCl(N₂)(PPh₃)₂, [IrCl(C₈H₁₄)₂]₂, and IrClL₂ (X = halide, L = tertiary phosphine or arsine) are excellent catalysts for the reactions of HSiR₃ (R = Ph, Et, OEt) with R′OH (R′ = Et, Me). With IrX(CO)L₂ the reactionis inhibited by an excess of HSiR₃ and by the product, H₂. The proposed mechanism involves intermediate formation of ClSiR₃ by elimination from the silyl complex IrHX(SiR₃)(CO)L₂. The iridium(I) complex IrH(CO)L₂, also formed in this step, reacts with HCl in the catalytic cycle or with H₂ or HSiR₃ in the inhibition reactions. The exchange reaction of HSiR₃ (R = OEt, Et) with D₂ is catalysed by IrCl(CO)(PPh₃)₂ or IrH₃(CO)(PPh₃)₂, and probably has a similar mechanism. Catalysis of the HSiR₃-R′OH reaction by the other iridium(I) complexes probably involves direct attack by the alcohol on the coordinated silyl group of the intermediate IrHCl(SiR₃)L₂.     

Copper-supported catalysts in methanol synthesis and water gas shift reaction

The comparative studies of physicochemical properties of Cu-support catalysts (support = ZnO, Al₂O₃, Cr₂O₃, ZnAl₂O₄, FeAlO₃, or CrAl₃O₆) and their catalytic activity in methanol synthesis and water gas shift reaction were the main goal of this work. The promotion effect of copper addition in both reaction was proved. The formation of spinel type structure CuCr₂O₄, ZnAl₂O₄ and binary oxide CrAl₃O₆, FeAlO₃ during calcination process was confirmed by XRD technique. Results showed that 20% Cu/FeAlO₃ had the best performance in water gas shift reaction. The best selective and active catalyst in methanol synthesis was 20% Cu/ZnAl₂O₄.     

On the mechanism of low-temperature water gas shift reaction on copper

Periodic, self-consistent density functional theory (DFT-GGA) calculations are used to investigate the water gas shift reaction (WGSR) mechanism on Cu(111). The thermochemistry and activation energy barriers for all the elementary steps of the commonly accepted redox mechanism, involving complete water activation to atomic oxygen, are presented. Through our calculations, we identify carboxyl, a new reactive intermediate, which plays a central role in WGSR on Cu(111). The thermochemistry and activation energy barriers of the elementary steps of a new reaction path, involving carboxyl, are studied. A detailed DFT-based microkinetic model of experimental reaction rates, accounting for both the previous and the new WGSR mechanism show that, under relevant experimental conditions, (1) the carboxyl-mediated route is the dominant path, and (2) the initial hydrogen abstraction from water is the rate-limiting step. Formate is a stable "spectator" species, formed predominantly through CO2 hydrogenation. In addition, the microkinetic model allows for predictions of (i) surface coverage of intermediates, (ii) WGSR apparent activation energy, and (iii) reaction orders with respect to CO, H2O, CO2, and H2.     

Cu-Pt-Au三元合金催化水煤气变换反应的密度泛函研究

利用密度泛函理论（DFT）研究了不同掺杂量的Cu-Pt-Au催化剂性质及水煤气变换反应（WGSR）在催化剂表面上的反应机理。首先对Cu-Au和Pt-Au二元催化剂的稳定性和电子活性进行研究,发现Pt-Au催化剂的协同效应较优,稳定性更优,结合能为77.15 eV,d带中心为-3.18 eV。当将Cu继续掺杂到Pt-Au合金中构成Cu-Pt-Au三元催化剂时,Cu₃-Pt₃-Au（111）结合能为77.99 eV,且d带中心为-3.05 eV,表明其具有较优的稳定性和电子活性。探讨了WGSR在Cu₃-Pt₃-Au（111）上的反应历程,氧化还原机理因CO氧化的能垒达到4.84 eV而不易进行。CHO和COOH两个中间体为竞争关系,且形成CHO中间物时的能垒较小,因此,反应相对容易按照甲酸机理进行。     

Spectroscopic demonstration of the formation of carbonyl compounds of iridium in reaction of iridium salts with formic acid

Conclusions On the basis of a study of the IR absorption spectra of the reaction products of iridium salts with formic acid, it was demonstrated that actually these compounds contain carbonyl groups, and not formic acid, as was earlier believed.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1114–1115, June, 1966.     

A theoretical study of metal-metal cooperativity in the homogeneous water gas shift reaction

The possibility of metal-metal cooperativity in improving the yield of the homogeneous water gas shift reaction (WGSR) has been investigated through full quantum mechanical density functional theory calculations. The calculations indicate that bimetallic catalysts would be likely to be more highly active than mononuclear metal-based catalysts for the WGSR. The results have implications for the design of improved WGSR catalysts in the future.     

MoO_x促进的Pt基催化剂用于低温水汽变换反应(英文)

通过浸渍还原法制备了不同比例的Pt-Mo/SiO_2催化剂,采用X射线衍射、透射电镜、X射线近边吸收谱和X射线光电子能谱表征了Pt-Mo/SiO_2催化剂的组成、结构及价态.研究结果表明,少量MoO_x修饰Pt-Mo/SiO_2催化剂在低温水汽变换反应中表现出比Pt/SiO_2催化剂更高的催化活性,过量MoO_x包覆的Pt-Mo/SiO_2催化剂活性较低.低温水汽变换反应活性来自于Pt与表面MoO_x的界面协同作用,限域在Pt纳米颗粒表面的MoO_x表现出较低价态,高分散MoO_x纳米岛修饰的Pt纳米颗粒是低温水汽变换反应的活性结构.     

Kinetics and catalysis by NaY entrapped Pt carbonyl clusters in the CO+NO reaction

[Pt₁₂(CO)₂₄]^2–/NaY and [Pt₉(CO)₁₈]^2–/NaY exhibited much higher activities in the CO+NO reaction at 473 K compared with Pt/Al₂O₃. Kinetic study andin-situ FTIR results suggest that NO adsorption is the rate-limiting step in the CO+NO reaction on intrazeolite Pt carbonyl clusters.     

On the mechanism of the chromium carbonyl photocatalyzed watergas shift reaction

The chromium hexacarbonyl catalyzed watergas shift reaction is accelerated by UV irradiation and inhibited by increased CO pressure. An activation energy of 30 kJ mol^?1 has been determined for the photochemical and one of 145 kJ mol^?1 for the thermal reaction. Light accelerates the conversion of Cr(CO)₆ into [Cr(CO)₅ formate]^?, which is thermally activated, as evidenced by in situ IR and UV spectroscopy.     

Ferrofluid catalyzed water gas shift reaction to give carbon-dioxide and hydrogen

A ferrofluid consisting of colloidally dispersed magnetite particles in water was found to be an efficient selective catalyst for water gas shift reaction at 15–25 atmosphere of CO pressure in the temperature range of 423–553 K where the products obtained were only CO₂ and H₂. The reaction was studied as a function of variation of the concentration of catalyst, pressure of CO gas and temperature. Kinetic parameters suggested a mechanism involving first order dependence in CO and catalyst concentrations.     

Efficient catalysis of a Diels-Alder reaction by metallo-vesicles in aqueous solution

Vesicles have been prepared from a cyclic phosphate ester (5,5-di-n-dodecyl-2-hydroxy-1,3,2-dioxaphosphorinan-2-one) with copper(II) counterions (Cu(dDP)(2)). They form a highly efficient aqueous Lewis acid catalyst system. The reaction of two azachalcon derivatives (1a, 1b) with cyclopentadiene (2) was studied to elucidate the catalytic potential of this system.     

不同金属催化水煤气变换反应活性的Monte Carlo模拟研究

运用BOC-MP方法对Cu(110),Cu(111),Pd(111)和Au(111)等过渡金属催化的WGS反应的可能微观动力学步骤进行了详尽的能学数据计算,并结合MonteCarlo方法对WGS反应的表面氧化还原机理进行了计算机模拟。结果表明,Cu的催化活性优于Pd,Au的催化活性,并获得了相应金属上WGS反应的表观活化能及动力学指前因子(相对值);在此基础上,对该反应的结构敏感性进行了研究,发现该反应为一结构敏感反应,与实验结果相符。     

For more and purer hydrogen-the progress and challenges in water gas shift reaction

The water gas shift(WGS) reaction is a standard reaction that is widely used in industrial hydrogen production and removal of carbon monoxide. The improved catalytic performance of WGS reaction also contributes to ammonia synthesis and other reactions. Advanced catalysts have been developed for both high and low-temperature reactions and are widely used in industry. In recent years, supported metal nanoparticle catalysts have been researched due to their high metal utilization. Low-temperature c...     

Chemical oxidation of water to dioxygen. Homogeneous catalysis by a ruthenium aquo-complex

Transition Metal Chemistry -     

Theoretical investigation of water gas shift reaction catalyzed by iron group carbonyl complexes M(CO)5 (M = Fe, Ru, Os)

We have investigated the mechanism of M(CO)(5) (M = Fe, Ru, Os) catalyzed water gas shift reaction (WGSR) by using density functional theory and ab initio calculations. Our calculation results indicate that the whole reaction cycle consists of six steps: 1 → 2 → 3 → 4 → 5 → 6 → 2. In this stepwise mechanism the metals Fe, Ru, and Os behave generally in a similar way. However, crucial differences appear in steps 3 → 4 → 5 which involve dihydride M(H)(2)(CO)(3)COOH(-) (4') and/or dihydrogen complex MH(2)(CO)(3)COOH(-) (4). The stability of the dihydrogen complexes becomes weaker down the iron group. The dihydrogen complex 4_Fe is only 11.1 kJ/mol less stable than its dihydride 4'_Fe at the B3LYP/II(f)++//B3LYP/II(f) level. Due to very low energy barrier it is very easy to realize the transform from 4_Fe to 4'_Fe and vice versa, and thus for Fe there is no substantial difference to differentiate 4 and 4' for the reaction cycle. The most possible key intermediate 4'_Ru is 38.2 kJ/mol more stable than 4_Ru. However, the barrier for the conversion 3_Ru → 4'_Ru is 23.8 kJ/mol higher than that for 3_Ru → 4_Ru. Additionally, 4'_Ru has to go through 4_Ru to complete dehydrogenation 4'_Ru → 5_Ru. The concerted mechanism 4'_Ru → 6_Ru, in which the CO group attacks ruthenium while H(2) dissociates, can be excluded. In contrast to Fe and Ru, the dihydrogen complex of Os is too unstable to exist at the level of theory. Moreover, we predict Fe and Ru species are more favorable than Os species for the WGSR, because the energy barriers for the 4 → 5 processes of Fe and Ru are only 38.9 and 16.2 kJ/mol, respectively, whereas 140.5 kJ/mol is calculated for the conversion 4' → 5 of Os, which is significantly higher. In general, the calculations are in good agreement with available experimental data. We hope that our work will be beneficial to the development and design of the WGSR catalyst with high performance.