Mono-Substitution of iron pentacarbonyl catalyzed by polynuclear iron carbonyl anions

The specific formation of LFe(CO)₄ (L = PPh₃, P(OPh)₃, P(OMe)₃ can be achieved by the reaction of Fe(CO)₅ with L in the presence of a catalytic amount of iron carbonyl anion. A convenient synthetic procedure was developed in which the iron carbonyl anion catalyst is generated in situ. It is shown that the mechanism does not proceed by the simple cleavage of the Fe₂(CO)₈^2? or Fe₃(CO)₁₁^2? anions, because triphenylphosphine reacts with these anions in the absence of Fe(CO)₅ to produce (PPh₃)₂Fe(CO)₃.     

五羰基铁催化羰化反应的研究进展

1827年,丹麦药剂师Zeise在加热PtCl2/KCl的乙醇溶液时得到了世界上第一个金属有机化合物,即后来人们命名的Zeise盐[1].1890年,Mond[1]等在研究一氧化碳（CO）对不锈钢阀门的腐蚀原因时发现：CO与镍粉反应生成的四羰基镍（Ni（CO）4）对阀门具有腐蚀作用．     

Photochemistry of iron pentacarbonyl adsorbed on titanium dioxide

The photolysis of iron carbonyl (Fe(CO)₅) adsorbed on titanium dioxide (TiO₂, anatase) was studied by FT-IR spectroscopy. When adsorbed Fe(CO)₅ is illuminated by visible and near-UV light, the IR spectrum of its photolysis products is hardly observed, indicating that most of the Fe(CO)₅ is photodecomposed to iron(0) or iron oxides on TiO₂. The carbon monoxide (CO) evolution rate upon illumination depends on the wavelength of light; 433 nm light is more effective for CO evolution than 366 nm light. This result implies that the band-gap excitation of TiO₂ has little effect on the photolysis of adsorbed Fe(CO)₅, since the absorption edge of TiO₂ (anatase) lies at around 400 nm. The effects of substrates on the photolysis of adsorbed Fe(CO)₅ are discussed with reference to previous results obtained for aluminium oxide (Al₂O₃) and silicon dioxide (SiO₂), on which the photolysis leads to the formation of Fe₂(CO)₉ or Fe₃(CO)₁₂.     

Reaction of iron pentacarbonyl with ethyl dichloroacetoacetate and dichloroacetylacetone

Conclusions Ethyl dichloroacetoacetate and dichloroacetylacetone react with Fe(CO)₅ to form iron chelates Fe[ClC · (COR)COCH₃]₃ (R=OEt and Me). The structures of these chelates were elucidated by³⁵Cl NQR, mass, and IR spectroscopy.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 478–479, February, 1985.     

Selective suppression of some radical reactions by iron pentacarbonyl

Conclusions On the example of the homolytic reaction of methallyl chloride with CCl₄ it was found that iron pentacarbonyl in catalytic amounts can selectively suppress the radical process involving chlorine atoms, and at the same time it catalyzes the chain reaction with trichloromethyl radicals, which act as carriers of the kinetic chain.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2320–2322, October, 1972.     

Iron isotope fractionation between liquid and vapor phases of iron pentacarbonyl

Iron isotope fractionation between liquid and vapor iron pentacarbonyl was measured in a closed system at ∼0 and ∼21 °C to determine if Fe isotope analysis of iron pentacarbonyl vapor is viable using electron-impact, gas-source mass spectrometry. At the 2σ level, there is no significant Fe isotope fractionation between vapor and liquid under conditions thought to reflect equilibrium. Experiments at ∼0 °C indicate iron pentacarbonyl vapor is ∼0.05 per mil (‰) greater in ⁵⁶Fe/⁵⁴Fe than liquid iron pentacarbonyl, which is just resolvable at the 1σ level. Partial decomposition of iron pentacarbonyl vapor or liquid to an iron oxide or iron metal shows that significant isotopic fractionation occurs, where the decomposed product has a lower ⁵⁶Fe/⁵⁴Fe ratio as compared to the starting iron pentacarbonyl. It follows that methods to decompose iron pentacarbonyl must be quantitative to obtain accurate isotope values.     

Stabilization of highly reactive cyclic polyolefins by coordination to iron carbonyls : Methylpentalenediiron pentacarbonyl

Thermolysis of (cis-bicyclo[6.1.0]nonatriene)diiron hexacarbonyl (FeFe) involves rearrangement of the starting organic moiety with formation of four iron carboyl complexes. The major product is the known cis-8,9-dihydroindeneiron tricarbonyl complex (VI). Two complexes have the same formula, C₉H₈Fe₂(CO)₅ (VII and VIII); VII can be also obtained by reaction of VI with Fe₂(CO)₉, while VIII is a methylpentalenediiron pentacarbonyl complex and represents a further example of stabilization of this reactive organic molecule by coordination; IX is probably a polycyclic cyclopentadienyl derivative [C₉H₉Fe(CO)₂]₂.Possible mechanisms for the formation of the four compounds are discussed.     

Reductive complexation of cycloheptatrienes by iron pentacarbonyl and catalytic sodium borohydride

Fe(CO)5 and a catalytic amount of sodium borohydride react with cycloheptatrienes in protic solvents to yield the corresponding tricarbonyl(eta 4-1,3-diene)iron complexes in a one-pot procedure, which has been found to be particularly efficient for the synthesis of the useful tricarbonyl(cyclo-heptadiene)iron complex.     

Anomalous behaviour of an allyl alcohol in reaction with iron pentacarbonyl

[(6,7,8,9-η)-Bicyclo[3.2.2]nona-2,6,8-trien-4-ol]tricabonyliron (6) rearranges in the presence of Fe(CO)₅ to [(2,3,6,7-η)-bicyclo[3.2.2]nona-2,6,8-trien-4-one] tricarbonyliron (7); rather than [(6,7,8,9-η)-bicyclo-[3.2.2]nona-6,8-dien-2-one] tricarbonyliron (9), the product expected on the basis of known organoiron chemistry and previously proposed mechanisms. The starting material 6 is stable in the absence of Fe(CO)₅, which leads to the conclusion that some iron-containing species derived from fe(CO)₅ is responsible for bringing about rearrangement. Since the usual mechanism for iron carbonyl-induced rearrangement in olefins cannot be operating here, a mechanism involving an ion pair with [HFe(CO)₄]^- is suggested.     

Anomalous dependence of particle size on supersaturation in the preparation of iron nanoparticles from iron pentacarbonyl

Anisotropic colloidal particles consisting of different compositions and geometry are useful for various applications. These include optical biosensing, antireflective coatings and electronic displays. In this work we demonstrate a simple and cost-effective method for fabricating anisotropic colloidal particles bearing a snowman-like shape. This is achieved by first settling the positively-charged polystyrene latex (PSL) colloids and negatively-charged silica colloids in deionized water onto a glass substrate, forming heterodoublets. The temperature is then raised above the glass transition temperature of the polymer. As a result, the silica particle spontaneously rises to the top of the PSL particle forming a snowman like structure. We have extended this method to different sizes and shown that the structure of the hybrid particles can be tuned by adjusting the size ratio between the silica and the PSL colloids. The surface coverage of the PSL, and hence of the snowman particles, on the glass substrate can also be varied by changing the ionic strength of the solution during the adhesion of PSL to the glass.     

Selective,iron pentacarbonyl catalyzed reduction of aryl iodides under mild conditions

Potassium tetracarbonylhydridoferrate, generated in situ from Fe(CO)₅/K₂CO₃ in methanol has been found to bring about catalytic reduction (up to 18 cycles) of aryl iodides under 1 atm carbon monoxide pressure. This reagent is specific for iodoaromatics, and tolerates the presence of several functionnal groups.     

Primary estimation of metal hydride electrode performance

A review on general electrochemical processes for metal hydride (MH) electrodes has been done. Fundamental MH electrode characteristics responsible for $ \left( - \right)\left. {{\text{M}}{{\text{H}}_x}{\text{/M}}} \right|\left. {6{\text{M}}\;{\text K}{\text{OH}}} \right|x{\text{Ni}}{\left( {\text{OH}} \right)_2}/x{\text{NiOOH}}\left( + \right) $ accumulator performance have been discussed in detail. Some examples of hydrogen storage alloys with permanent interest as MH electrodes have been presented.