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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.
Cyclization of the pyruvyl(methoxycarbonyl)tetracarbonyliron complex cis-(CO)4Fe[C(O)C(O)CH3](CO2CH3) induced by pronucleophile reagents
Gabon, Patrice,Sellin, Murielle,Salaün, Jean-Yves,Patinec, Véronique,Des Abbayes, Hervé,Kubicki, Marek M.
, p. 2196 - 2202 (2002)
Two iron complexes, cis-(CO)4Fe[C(O)C(O)CH3](CO2CH3) (1a) and cis-(CO)4Fe[C(O)CO2-CH2] [C(O)CH2] (3), are reported. Each complex can be considered as a λ-keto ester with a metal atom inserted into the chain linking its two organic groups. 1a is the only one found to evolve thermally, similarly to organic λ-keto esters, into the methoxy metallalactone (CO)4FeC(O)C(CH3)(OCH3)OC(O) (2a). This reaction is not reversible and does not require any acid or alkaline catalysis. The process does not result from a spontaneous dissociation of the methoxycarbonyl ligand of la but from an associative intra or intermolecular mechanism. A similar process can also be induced by pronucleophile reagents, and it affords a series of substituted metallalactones: (CO)4FeC(O)C(CH3)(Nu)OC(O) (Nu = OCH3 (2a), OC2H5 (2b), SC2H5 (2c), P(C6H5)2 (2d), P(C6H11)2 (2e)). Complex 2e has been characterized structurally. These substituted lactones are formed by nucleophilic attack of the reagent at the pyruvyl β-carbonyl followed by carbonylate attack on the alkoxycarbonyl ligand.
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.
Oriented long single walled carbon nanotubes on substrates from floating catalysts
Huang, Shaoming,Cai, Xianyu,Du, Chunsheng,Liu, Jie
, p. 13251 - 13254 (2003)
A new and feasible method to prepare long and well-oriented SWNTs on substrates in large scale is developed by applying a floating catalyst chemical vapor deposition (CVD) process. The catalysts for SWNT growth come from the decomposition of iron pentacarbonyl (Fe(CO)5) formed in situ from the reaction of iron powder and carbon monoxide gas. The growth of SWNTs is found to happen both on the substrate and in the gas flow. Both long and short nanotubes are formed on the substrates but only the long SWNTs are aligned by gas flow. The growth direction and the density of the long SWNTs can be easily controlled. In addition, long SWNTs can be cut and patterned using photolithography and water plasma etching techniques, offering a way to prepare patterned SWNTs with controllable orientation, density and lengths for various applications.
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
Bimetallic Iron-Rhodium Anionic Carbonyl Clusters: x>-(x=10 or 11), 2-, 2-, and -
Ceriotti, Alessandro,Longoni, Giuliano,Pergola, Roberto Della,Heaton, Brian T.,Smith, David O.
, p. 1433 - 1440 (1983)
The synthesis and chemical behaviour of the new iron-rhodium anionic carbonyl clusters x>- (x=10 or 11), 2-, 2-, and - are reported.Low-temperature mu
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.
THE INFRA-RED LASER-INDUCED PHOTOCHEMISTRY OF Fe(CO)4
Poliakoff, Martyn
, p. 217 - 222 (1987)
A brief summary of the IR photochemistry of matrix isolated Fe(CO)4 is presented.We explain how some of the processes can be rationalised on the distortion octahedron model, originally developed by considering the Jahn-Teller distortion of Fe(CO)4.An analogy is drawn, for the first time, between the reactions of Fe(CO)4 and haemoglobin.