Monometallic iron catalysts

2) Addition of iron complexes to rhodium or ruthenium hydroformylation catalysts in order to achieve synergistic effects. 

Iron Complexes as Additives to Conventional Hydroformylation Catalysts 

The screening of heterobimetallic hydroformylation catalysts with iron as one constituent received more attention than the use of monometallic Fe catalysts [9]. Earlier attempts were encouraged by the assumption that iron carbonyls, which can be formed in steel autoclaves under carbon monoxide, act as poisons for cobalt or rhodium catalysts [10]. Especially, the property of Fe(CO)5 to catalyze the aldol condensation of product aldehydes was considered to be detrimental to hydroformylation. Usually, this problem is solved either by technological means (fast separation of the product) or by the addition of chelating agents for iron [11]. 

A similar effect was observed with mixed iron-rhodium carbidocarbonyl clusters on oxide supports [14]. Trzeciak and Ziotkowski added Fe(CO)5 to Rh(acac)(CO)L (acac = acetylacetonate) [L=PPh3, P(OPh)3, P(N(C4H4)3)] and achieved in the hydroformylation of 1-hexene at a syngas pressure of 10 atm and 80 C an increase of up to 70% in the yield of the aldehyde [15]. The 

Besides interstitial carbon atoms, nitride groups have also been used to stabilize the cluster structure of iron-rhodium and iron-iridium hydroformylation catalysts [18]. 

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Iron-ruthenium bimetallic catalysts have also received considerable attention as interesting catalysts in Fischer-Tropsch synthesis [115,116]. It has been reported that the Fe-Ru alloy system results in catalysts that are more stable than monometallic iron catalysts [117], and that the hydrocarbon product distribution in CO hydrogenation can easily be modified when changing the relative proportions of the two metals [118]. 

In addition, some results on monometallic iron and bimetallic nickel-iron catalysts are reported to illustrate the general suitability of the presented cyanide method. 

Very recently Geus and co-workers [44, 45] have applied another method based on chemical complexes. This is the complex cyanide method to prepare both monocomponent (Fe or Co) and multicomponent Fischer-Tropsch catalysts. A large range of insoluble complex cyanides are known in which many metals can be combined, e.g. iron(n) hexacyanide and iron(m) hexacyanide can be combined with iron ions, but also with nickel, cobalt, copper, and zinc ions. Soluble complex ions of molybdenum(iv) which can produce insoluble complexes with metal cations are also known. Deposition precipitation (Section A.2.2.1.5) can be performed by injection of a solution of a soluble cyanide complex of one of the desired metals into a suspension of a suitable support in a solution of a simple salt of the other desired metal. By adjusting the cation composition of the simple salt solution, with a same cyanide, it is possible to adjust the composition of the precursor from a monometallic oxide (the case when the metallic cation is identical to that contained in the complex) to oxides containing one or several foreign elements. 

An interesting application of adsorption microcalorimetry was used by these researchers to examine changes in adsorption behavior of graphite-supported iron/rhodium bimetallic catalysts as a function of oxidation and reduction treatments. The differential heat of oxygen adsorption on the bimetallic catalysts after various treatments was compared to the values obtained for the monometallic materials to determine the relative contributions to the total adsorption. Reduction at 673 K produced an alloy whose... 

In this paper a study is presented on the preparation of a series of supported catalysts by precipitation of metal cyanide complexes in the presence of suspended supports. As supports alumina, titania, and silica, have been used. The metals studied comprise iron, cobalt, nickel, copper, manganese, palladium, and molybdenum. Both monometallic, bimetallic and even trimetallic cyanides were precipitated. The stoichiometry of the precipitated complexes was controlled by the valency of the metal ions and by using both nitroprusside and cyanide complexes. Electron microscopy was used to evaluate the distribution of the deposited complex cyanides on the supports. 57Fe-M6ssbauer spectra were measured on the dried precipitated complexes to gain information on the chemical composition of the iron containing complexes. 

The presence of thallium(0) led to an increase in activity and selectivity of metallic palladium catalysts supported on silica in aldose oxidation reactions. However, silica-supported thallium(0) had no activity by itself (entry 3). ° Similarly, the bimetallic catalyst platinum-thallium/ZSM-5, prepared by impregnation of thallium sulfate and chloroplatinic acid on Zeolite Socony Mobil-5 (ZSM-5), showed greater selectivity in propane aromatisation and almost the same catalytic activity as monometallic thallium/ZSM-5 (entry 4). Similar comparison of vanadium-caesium-copper and vanadium-caesium-copper-thallium catalysts supported on TiOa.SiC demonstrated that addition of thallium improved the catalytic activity in partial oxidation of p-tert-butyltoluene to p-tert-butyl-benzaldehyde (entry The application of solid-supported thallium-based catalysts in different processes includes (a) iron-thallium catalysts in carbon monoxide hydrogenations to form hydrocarbons and alcohols, and catalytic reforming of... 

Based on the research results of monometallic catalysts, scientists also studied on bimetallic catalysts for N2 activation. They realized that the adsorption energy of N2 determines the catalysts properties. Under specific reaction conditions, it can estimate adsorption energy of N2 on catalyst. The catalytic efficiency of the elements for the synthesis and decomposition of ammonia was correlated with the chemisorption energy of nitrogen. An inverted parabolic function (volcano curve) was obtained by Ozaki et in which iron, ruthenium, and osmium mark the top of the volcano. 

Thus, the CO ligand can be reduced to methyl this is a kind of monometallic model for the heterogeneous Fischer-Tropsch reaction, i.e. reduction of CO by H2 to alkanes using iron metal as catalyst (see Chap. 20.3). 

Schemes 58-62. A new non-rigid phosphine ligand was synthesized and reacted with Fe(CO)5 to form the mononuclear iron complex (Equation (81)). Phosphino-oxazoline ligands were used as assembling ligands for hetero-metallic complexes, where the phosphorus atom binds to iron and the nitrogen atoms act as donor atoms to copper, cobalt, or palladium (Scheme 58). The copper complex catalyzes cyclopropanation and Diels-Alder reactions. When 2-(A -diphenylphosphinomethyl-A -cyclohexyl)aminopyridine (NNP) reacts with Fe(CO)5 in ethanol, /ra .r-(OC)3Fe(NNP)2 is formed (Scheme 59). This monometallic complex can then be reacted with a copper salt in CH2GI2 to form a complex having an Fe-Cu dative bond. The complex was demonstrated to be an efficient catalyst for the cyclopropanation of styrene by ethyl diazoacetate and for the Diels-Alder reaction of cyclopentadiene and methacrolein. No other heterometallic complexes have been shown to have such reactivity. Previously known...

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