13463-40-6Relevant articles and documents
Extraction and recovery characteristics of Fe element from Nd-Fe-B sintered magnet powder scrap by carbonylation
Miura, Koji,Itoh, Masahiro,Machida, Ken-Ichi
, p. 228 - 232 (2008)
Iron element was extracted from the powder scrap of Nd-Fe-B sintered magnets via the carbonylation reaction with sulfur as a catalyst. The resultant carbonyl complex was Fe(CO)5 and the yield was evaluated to be ～56% by energy dispersion X-ray analysis. After applying the hydrogenation disproportionation treatment on the powder scrap, the extraction rate for Fe element was considerably accelerated on the resultant α-Fe/Fe2B/NdH2 (or neodymium oxides) nanocomposite powders to produce Fe(CO)5 in a maximum yield of ～92%.
Coordination chemistry and oxidative addition of trifluorovinylferrocene derivatives
Heinrich, Darina,Schmolke, Willi,Lentz, Dieter
, p. 105 - 112 (2016)
Complexes using trifluorovinylferrocene and 1,1′-bis(trifluorovinyl)ferrocene as ligands can be obtained by the reaction with a series of fragments of transition metal complexes. Formation of [Pt(η2-trifluorovinylferrocene)(PPh3)2] (1), [{Pt(PPh3)2}2(η2-1,1′-bis(trifluorovinyl)ferrocene)] (2) and [Pt(η2-1,1′-bis(trifluorovinyl)ferrocene)(PPh3)2] (3) were achieved by ligand substitution in [Pt(η2-CH2?=?CH2)(PPh3)2]. Treatment of eneacarbonyldiiron with trifluorovinylferrocene provided [Fe(CO)4(η2-trifluorovinylferrocene)] (4). Photolytically activated reactions of [MnCp(CO)3] and [MnCp′(CO)3] (Cp′?=?C5H4CH3) afforded [MnCp(CO)2(η2-trifluorovinylferrocene)] (5a) and [MnCp′(CO)2(η2-trifluorovinylferrocene)] (5b) respectively. [Ni(η2-trifluorovinylferrocene)(Cy2P(CH2)2PCy2)] (6) could be obtained by reaction with [Ni(COD)2] and Cy2P(CH2)2PCy2. Furthermore the C[sbnd]F bond activation by oxidative addition in the presence of lithium iodide yielding two isomers of [PtI{η1-difluorovinylferrocene}(PPh3)2] (7a/7b) is presented. Molecular structures of 1, 4 and 7a were elucidated using X-ray single crystal diffraction. The spectroscopic and structural data of these complexes prove the powerful π acceptor abilities of these ligands.
The wavelength dependence of excimer laser photolysis of Fe(CO)5 in the gas phase. Transient infrared spectroscopy and kinetics of the Fe(CO)x (x = 4,3,2) photofragments
Seder, T. A.,Ouderkirk, A. J.,Weitz, Eric
, p. 1977 - 1986 (1986)
The transient infrared absorption spectra of the coordinatively unsaturated Fe(CO)x species generated via excimer laser photolysis of gas phase Fe(CO)5 are presented and discussed.The photofragments produced upon 351, 248, and 193 nm photolysis are characterized.Fe(CO)3 and Fe(CO)4 are produced upon 351 nm photolysis.In addition to these two fragments, Fe(CO)2 is produced on 248 nm photolysis.The gas phase structures of these Fe(CO)x fragments are observed to be compatible with those determined from condensed phase experiments.The coordinatively unsaturated photofragments are typically formed with significant amounts of internal excitation.The rate constants for reaction of Fe(CO)4, Fe(CO)3, and Fe(CO)2 with CO are (3.5+/-0.9)X1010, (1.3+/-0.2)X1013, and (1.8+/-0.3)X1013 cm3 mol-1 s-1, respectively.The large difference in the magnitude of the rate constant for reaction of Fe(CO)4 vs Fe(CO)3 and Fe(CO)2 with CO is rationalized in terms of the spin states of the reactants and products.Following 193 nm photolysis, a new product is observed which is tentatively assigned as an excited electronic state of Fe(CO)3.A photochemical scheme which accounts for all observed products is presented.
Methyl transfer to nucleophilic metal carbonylate anions in catalytic methanol homologation
Roth, Stanley A.,Stucky, Galen D.,Feder, Harold M.,Chen, Michael J.,Rathke, Jerome W.
, p. 708 - 714 (1984)
The kinetics of the stoichiometric reaction of methyltrialkylammonium cations with nucleophilic metal carbonylate anions was investigated in terms of its relationship to a new catalytic methanol homologation method. At high temperatures and pressures of H2 and CO, a methyl group from each cation is incorporated into methane or ethanol. In the ionizing solvent, N-methylpyrrolidinone, the reaction using iron tetracarbonyl hydride anion is first order in both the methylammonium cation and iron carbonylate anion concentrations and zero order with respect to the partial pressures of hydrogen or carbon monoxide. The enthalpy and entropy of activation, in the temperature range of 180-210°C, are 44 kcal/mol and +17 eu, respectively. The second-order rate constants exhibit a primary kinetic salt effect, increasing with decreasing salt concentration. The rate constants also increased with decreasing dielectric constant of the solvent. The data are consistent with methyl group transfers (SN2) between ions as the rate-limiting step. At 200°C and 245 atm (3:1 CO/H2) the second-order rate constants, 2.0 × 10-4 M-1 s-1 for HFe(CO)4-, 5.3 × 10-4 M-1 s-1 for Mn(CO)5-, are a measure of the nucleophilicities of these carbonylates toward tetramethylammonium ion. In the case of the manganate system, the product selectivity (ethanol vs. methane) was found to be independent of H2 or CO partial pressure between 61 and 184 atm but slightly dependent on the concentration of Mn(CO)5-. These factors are discussed in terms of reaction mechanism.
Synthesis of the Ethyl Oxalyl Tetracarbonyl Iron Anion -, its Methylation at the Metal into (CO)4Fe(Me)(COCO2Et) and Further Carbon-Carbon Coupling into Ethyl Pyruvate
Sabo-Etienne, Sylviane,Larsonneur, Anne-Marie,Abbayes, Herve des
, p. 1671 - 1673 (1989)
The stable anion - (2) is methylated at the metal by reaction with MeSO3CF3 at -50 deg C to give (CO)4Fe(Me)(COCO2Et) (3) characterized in situ by 1H and 13C NMR; at -30 deg C
Aime, Silvio,Osella, Domenico
, p. 207 - 210 (1982)
Chemistry of the Metal Carbonyls. Part 81. Homonuclear and Heteronuclear Di- and Tri-metal Carbonyl Complexes derived from Dicarbonyl(pentamethylcyclopentadienyl)rhodium; X-ray Crystal Structure of
Aldridge, Mark L.,Green, Michael,Howard, Judith A. K.,Pain, Geoffrey N.,Porter, Simon J.,et al.
, p. 1333 - 1340 (1982)
Treatment of with (thf=tetrahydrofuran) affords , the structure of which has been determined by an X-ray diffraction study.The crystals are orthorhombic, space group Pnam (non-standard setting of Pnma, No. 62), in a unit cell with a=16.851(12), b=9.338(5), c=11.566(9) Angstroem, U=1820(2) Angstroem3 at 220 K, and Z=4.The structure was solved to R 0.057 (R' 0.058) from 1860 observable independent reflections 3.0?(l)>.The molecule possesses Cs symmetry; one terminal carbonyl ligand on each of the metal atoms, together with the Rh-Mn bond , define the mirror plane.The cyclopentadienyl ligand on the Mn atom is in a trans relationship to the pentamethylcyclopentadienyl ligand on the Rh atom and both lie astride (perpendicular to) the mirror plane.The two other carbonyl ligands are terminal to the Mn atom but are strongly semi-bridging to the Rh atom and define planes which are nearly perpendicular to the mirror plane.A distortion of the Rh-C5 geometry towards a 'diolefin' type attachment is discussed.Reaction of with in thf affords the compounds and .The latter is also formed, together with 3-CO)(μ-CO)2(CO)3(η-C5Me5)2>, on treatment of with excess .The trirhodium complex 3-CO)(μ-CO)2(η-C5Me5)2> was obtained in high yield by pyrolysis of acd undergoes dynamic behaviour in solution.Protonation of the trirhodium cluster of affords quantitatively the cation 3-CO)(μ-CO)2(η-C5Me5)3>(1+) which can be deprotonated with NaOMe in MeOH.
Phosphorus-carbon bond forming reactions of iron tetracarbonyl-coordinated phosphenium ions
King, Ryan C.,Nilewar, Shrikant,Sterenberg, Brian T.
, p. 68 - 74 (2019)
Abstraction of chloride from [Fe(CO)4(PPh2Cl)] (1) in the presence of PPh3 leads to [Fe(CO)4(PPh2(PPh3))][AlCl4] (2), an iron complex of a phosphine-coordinated phosphenium ion. The PPh3 is readily displaced by ferrocene, leading to an electrophilic aromatic substitution reaction, and formation of [Fe(CO)4{PPh2Fc}] (3) (Fc = ferrocenyl). Alternately, chloride abstraction from 1 in the presence of ferrocene leads directly to 3, via a transient phosphenium ion complex. The transient phosphenium ion complex also reacts with N,N-diethylaniline, indole, and pyrrole to form the respective p-anilinyl, 3-indolyl, and 2-pyrryl phosphine complexes via electrophilic aromatic substitution. Chloride abstraction from [Fe(CO)4(PPhCl2)] in the presence of ferrocene leads to a double substitution reaction, forming [Fe(CO)4{PPhFc2}] (13).
Synthesis and characterization of high-spin [(CO)3FeII(CO2R)3]2Fe II complexes formed by thermolysis of cis-(CO)4Fe(CO2R)2 (R = Me, t-Bu, allyl, 1,1′-dimethylallyl). X-ray crystal structure of the allyl derivative
Le Gall, Nathalie,Luart, Denis,Salaün, Jean-Yves,Talarmin, Jean,Des Abbayes, Hervé,Toupet, Lo?c,Menendez, Nieves,Varret, Fran?ois
, p. 1775 - 1781 (2002)
Instead of the expected carbon-carbon coupling into oxalates, thermolysis at 30 °C of the cis-bis(alkoxycarbonyl) monomers (CO)4Fe(CO2R)2 (1) affords the novel trimetallic compounds [(CO)3Fe(μ,η2-CO2R)3]2 Fe (R = Me (2a), t-Bu (2b), allyl (2c), 1,1′-dimethylallyl (2d)). As shown by 1H and 13C NMR, these complexes 2, which can be described as a central Fe(II) surrounded by two [(CO)3Fe(CO2R)3]- ligands, are paramagnetic. A Mo?ssbauer study of 2a and 2d revealed that these complexes display a high-spin configuration of their central iron atom and a low-spin configuration of the two lateral iron atoms. The easy formation of these complexes 2 by reacting fac-[(CO)3Fe(CO2R)3]- anions with FeCl2 suggests that formation of 2 by thermal evolution of 1 could occur via an associative mechanism, giving rise to the [(CO)3Fe(CO2R)3] pattern. Further thermolysis of 2 at 50 °C affords alcohols, Fe(CO)5, carbon monoxide, and bis(alkyl carbonates).
Lewis base character of hydroxygermylenes for the preparation of heterobimetallic LGe(OH)M systems (M = Fe, Mn, L = HC[(CMe)(NAr)]2, Ar = 2,6-iPr2C6H3)
Pineda, Leslie W.,Jancik, Vojtech,Colunga-Valladares, Juan F.,Roesky, Herbert W.,Hofmeister, Anja,Magull, Joerg
, p. 2381 - 2383 (2006)
LGeOH (1; L = HC[(CMe)(NAr)]2, Ar = 2,6-iPr2C 6H3) reacted with iron and manganese complexes to give LGe(OH)Fe(CO)4 (2) and LGe(OH)Mn(Cp)(CO)2 (3; Cp = cyclopentadienyl). Compounds 2 and 3
Osella, Domenico,Botta, Mauro,Gobetto, Roberto,Amadelli, Rossano,Carassiti, Vittorio
, (1988)
Vessieres, A.,Touchard, D.,Dixneuf, P.
, p. 93 - 100 (1976)
Davison, A.,Traficante, D. D.,Wreford, S. S.
, (1972)
Reactions of 1,1,3,3-tetramethyldisilazane with dicobalt octacarbonyl and iron pentacarbonyl. Thermal decomposition of the cobalt and iron carbonyl silazane complexes
Semenov,Ladilina,Khorshev,Makarenko,Kurskii,Bochkova
, p. 2455 - 2462 (1998)
The reaction of (HMe2Si)2NH with Co2(CO)8 gives the complex [Co2(CO)7(SiMe2)2NH 2]+[Co(CO)4]-. Its thermal decomposition starts with dissociation into the acid HCo(CO)4 and the base Co2(CO)7(SiMe2)2NH. After that, the base and the initial complex decompose further under the action of HCo(CO)4. The final products of this reaction are CO, NH3, Co, volatile dimethylcyclosilazane, and a solid residue consisting of cobalt particles encapsulated into a polymethylsiloxane matrix and possessing properties of mixed para-and ferromagnetics with an ultimate specific magnetization of 64-74 G g-1. Tetramethyldisilazane reacts with iron pentacarbonyl under UV irradiation to give relatively stable 1,3-bis(tetracarbonylhydrideiron)-1,1,3,3-tetramethyldisilazane. This product contains Fe - H...N hydrogen bonds, which stabilize it against dehydrogenation and cyclization to diironcyclodisilazane. Thermal decomposition of this product was investigated.
Protonation and electrochemical properties of a bisphosphide diiron hexacarbonyl complex bearing amino groups on the phosphide bridge
Shimamura, Takehiko,Maeno, Yuki,Kubo, Kazuyuki,Kume, Shoko,Greco, Claudio,Mizuta, Tsutomu
, p. 16595 - 16603 (2019)
A bisphosphide-bridged diiron hexacarbonyl complex 3 with NEt2 groups on the phosphide bridge was synthesized to examine a new proton relay system from the NEt2 group to the bridging hydride between the two iron centers. As a precurs
Brodie, A. M.,Johnson, B. F. G.,Lewis, J
, (1973)
Addition of electrophiles to metalladiborane anions 2-B2H5)>- (Fe, Ru, Os)
Coffy, Tim J.,Shore, Sheldon G.
, p. C27 - C30 (1990)
Addition of the electrophiles (CH3)+, H+, + to the metalladiborane anions 2-B2H5)>- (M = Fe, Ru, Os) has been investigated.Addition occurs at the metal center.The complexes CH3Os(CO)4(η2-B2H5), HM(CO)4(η2-B2H5) (M = Ru, Os) and (PPh3)AuM(CO)4(η2-B2H5) (M = Fe, Ru, Os) have been formed.NMR spectra of HM(CO)4(η2-B2H5) indicate that the H atom on the metal is cis to the B2H5 ligand.Relative stabilities of the complexes LM(CO)4(η2-B2H5) are in the order M = Os > Ru > Fe for a given electrophile and the order L = (Ph3P)Au > H for a given metal.
Kane, V. V.,Light, J. R. C.,Whiting, M. C.
, p. 533 - 538 (1985)
A new approach to studying the mechanism of catalytic reactions: An investigation into the photocatalytic hydrogenation of norbornadiene and dimethylfumarate using polyethylene matrices at low temperature and high pressure
Childs,Cooper,Nolan,Carrott,George,Poliakoff
, p. 6857 - 6866 (2001)
This paper presents a new method for investigating the mechanisms of homogeneously catalyzed reactions involving gases, particularly H2. We show how the combination of polyethylene (PE) matrices and high pressure - low temperature (HPLT) experiments can be used to provide new mechanistic information on hydrogenation processes. In particular, we show how we are able to generate reaction intermediates at low temperature, and then to extract the contents of the PE film at room temperature to characterize the organic products using GC-MS. We have used our new technique to probe both the hydrogenation of dimethyl fumarate (DF), using Fe(CO)4(η2-DF) as the catalytic species, and the hydrogenation of norbornadiene (NBD), using (NBD)M(CO)4 (M = Cr or Mo) as the catalytic species. Irradiation of Fe(CO)4(η2-DF) in a PE matrix at 150 K resulted in the formation of an intermediate complex tentatively assigned Fe(CO)3(η4-DF). Warming this complex to 260 K under H2 leads to the formation of Fe(CO)3(η2-DF)(η2-H2). Further warming of the reaction system results in the hydrogenation of the coordinated DF, to generate dimethyl succinate (DS). Characterization of the intermediate species was obtained using FTIR spectroscopy. Formation of DS was confirmed using both FTIR spectroscopy and GC-MS analysis. UV photolysis of (NBD)M(CO)4 in PE under H2 in the presence of excess NBD results in the formation of the hydrogenated products norbornene (NBN) and nortricyclene (NTC), with trace amounts of norbornane (NBA) being observed. These products were in similar ratios to those observed in fluid solution. However, for (NBD)Mo(CO)4, the relative amounts of the organic products change considerably when the reaction is repeated in PE under H2 in the absence of free NBD, with NBA being the major product. The use of our HPLT cell allows us to vent and exchange high pressures of gases with ease, and as such we have performed gas exchange reactions with H2 and D2. Analysis of the reaction products from these exchange reactions with GC-MS provides evidence for the mechanism of formation of NBA, in both the presence and absence of excess NBD, a reaction which has been largely ignored in previous studies.
Reactions of Fe(CO)5 and H2Fe(CO)4 Related to the Water-Gas Shift Reaction
Pearson, Ralph G.,Mauermann, Hieko
, p. 500 - 504 (1982)
The reaction of Fe(CO)5 with base to form HFe(CO)4- has a rate-determining step Fe(CO)5 + OH- -> Fe(CO)4COOH- (k1) at high base concentration with k1 = 70 M-1 s -1 at 25 deg C in 70:30 methanol-water.At low base concentration the rate-determining step is Fe(CO)4CO22- -> Fe(CO)42- + CO2 (k3), with the observed rate depending on the square of the total base concentration.The thermal decomposition of H2Fe(CO)4 has a rate-determining step of H2Fe(CO)4 -> H2 + Fe(CO)4 and a stoichiometry in 70:30 methanol-water of 4H2Fe(CO)4 -> 3H2(*) + H2Fe3(CO)11 + Fe(CO)5.In the water-gas shift reaction, Fe(CO)5 is a poor catalyst because of the conficting pH requirements of the two cyclic processes.
Adams, Richard D.,Babin, James E.,Estrada, Javier,Wang, Jin-guu,Hall, Michael B.,Low, Arthur A.
, p. 1885 - 1890 (1989)
Hill, Anthony F.,Nasir, Bashir A.,Stone, F. Gordon A.
, p. 179 - 188 (1989)
Ring closure of alkoxycarbonyl(tetracarbonyl)pyruvoyliron complexes into metallalactones induced by nucleophilic attack of carbanions
Cabon, Patrice,Rumin, Rene,Salauen, Jean-Yves,Des Abbayes, Herve,Triki, Smail
, p. 1515 - 1524 (2006)
The reaction of carbanions with the pyruvoyl-substituted iron complex [(CO)4Fe(CO2CH3){C(O)C(O)CH3}] (1) affords the anionic trifunctionalized metallalactones [(CO)3Fe{C(O) C(CH3)(CRR′R″)OC4(O)(Fe-C4)} (CO2CH3)]- (3), whose formation results from the addition of the nucleophile to the β carbonyl of the pyruvoyl moiety, followed by attack of the oxygen of this β carbonyl on a terminal carbonyl ligand. These anionic lactones react, at low temperature, with HCl to give rise to the neutral lactones [(CO)4Fe{C(O)C(CH3) (CRR′R″)OC4(O)(Fe-C4)}] (2), which were previously obtained by addition of NuH nucleophiles to 1. Complex 3(3), whose lactonic ring formation has been performed using the diethyl malonate anion (R = R′ = CO2C2H5; R″ = H), and the dimethyl-substituted neutral lactone 2(1) (R = R′ = R″ = H) have been characterized by X-ray diffraction studies. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.
Iron Catalyzed Hydroformylation of Alkenes under Mild Conditions: Evidence of an Fe(II) Catalyzed Process
Pandey, Swechchha,Raj, K. Vipin,Shinde, Dinesh R.,Vanka, Kumar,Kashyap, Varchaswal,Kurungot, Sreekumar,Vinod,Chikkali, Samir H.
supporting information, p. 4430 - 4439 (2018/04/05)
Earth abundant, first row transition metals offer a cheap and sustainable alternative to the rare and precious metals. However, utilization of first row metals in catalysis requires harsh reaction conditions, suffers from limited activity, and fails to tolerate functional groups. Reported here is a highly efficient iron catalyzed hydroformylation of alkenes under mild conditions. This protocol operates at 10-30 bar syngas pressure below 100 °C, utilizes readily available ligands, and applies to an array of olefins. Thus, the iron precursor [HFe(CO)4]-[Ph3PNPPh3]+ (1) in the presence of triphenyl phosphine catalyzes the hydroformylation of 1-hexene (S2), 1-octene (S1), 1-decene (S3), 1-dodecene (S4), 1-octadecene (S5), trimethoxy(vinyl)silane (S6), trimethyl(vinyl)silane (S7), cardanol (S8), 2,3-dihydrofuran (S9), allyl malonic acid (S10), styrene (S11), 4-methylstyrene (S12), 4-iBu-styrene (S13), 4-tBu-styrene (S14), 4-methoxy styrene (S15), 4-acetoxy styrene (S16), 4-bromo styrene (S17), 4-chloro styrene (S18), 4-vinylbenzonitrile (S19), 4-vinylbenzoic acid (S20), and allyl benzene (S21) to corresponding aldehydes in good to excellent yields. Both electron donating and electron withdrawing substituents could be tolerated and excellent conversions were obtained for S11-S20. Remarkably, the addition of 1 mol % acetic acid promotes the reaction to completion within 16-24 h. Detailed mechanistic investigations revealed in situ formation of an iron-dihydride complex [H2Fe(CO)2(PPh3)2] (A) as an active catalytic species. This finding was further supported by cyclic voltammetry investigations and intermediacy of an Fe(0)-Fe(II) species was established. Combined experimental and computational investigations support the existence of an iron-dihydride as the catalyst resting state, which then follows a Fe(II) based catalytic cycle to produce aldehyde.
