12002-28-7Relevant academic research and scientific papers
HYDROGENATION OF N-BENZYLIDENEANILINE WITH MOLECULAR HYDROGEN USING IRON PENTACARBONYL AS CATALYST PRECURSOR
Radhi, Mazin A.,Marko, Laszlo
, p. 359 - 364 (1984)
N-benzylideneaniline is hydrogenated to N-benzylaniline by H2 in the presence of Fe(CO)5, as catalyst precursor, in alcohol solution at 150 deg C and about 100 bar H2 pressure.The reaction is inhibited by CO.In a stoichiometric reaction, H2Fe(CO)4 hydroge
Molecular structure of tetracarbonyldihydroiron: Microwave measurements and density functional theory calculations
Drouin, Brian J.,Kukolich, Stephen G.
, p. 6774 - 6780 (1998)
Microwave spectra of seven isotopomers of tetracarbonyldihydroiron were measured in the 4-16 GHz range using a Flygare-Balle type microwave spectrometer. Measured transitions were fit using a rigid rotor Hamiltonian with five independent distortion constants. Structural parameters from a least-squares fit to the rotational constants are r(Fe-H) = 1.576(64) ?, r(Fe-C1) = 1.815(54) ?, r(Fe-C3 = 1.818(65) ?, r(C1-O1) = 1.123(80) ?, r(C3-O3) = 1.141(74) ?, ?, and this indicates that the complex is clearly a 'classical dihydride' rather than an η2-'dihydrogen' complex. Structural parameters obtained from a density functional theory calculation agreed with measured values to within 2%. The density functional theory analysis of the anharmonicity in the Fe-H symmetric stretching potential is shown to support the observed deuterium isotope effects observed for the hydrogen atom coordinates. The anharmonicity effects are larger for the Fe-H stretching coordinate than for the 0(Fe-D) bond lengths were observed to be 0.05(4) ? shorter than the r0(Fe-H) bond lengths.
A Combined theoretical and experimental study on the role of spin states in the chemistry of fe(co)5 photoproducts
Cowan, Alexander J.,George, Michael W.,Portius, Peter,Besora, Maria,Carreon-Macedo, Jose-Luis,Harvey, Jeremy N.,Ronayne, Kate L.,Sun, Xue-Zhong,Towrie, Michael
, p. 3583 - 3592 (2009)
A combined experimental and theoretical study is presented of several ligand addition reactions of the triplet fragments 3Fe(CO) 4 and 3Fe(CO)3 formed upon photolysis of Fe(CO)5. Experimental data are
Reaction Kinetics of Coordinatively Unsaturated Iron Carbonyls Formed on Gas-Phase Excimer Laser Photolysis of Fe(CO)5
Ryther, Robert J.,Weitz, Eric
, p. 9841 - 9852 (1991)
The reactions of species produced on gas-phase excimer laser photolysis of Fe(CO)5 have been followed by transient infrared spectroscopy employing a diode laser probe.The initial photoproducts formed on 193-nm photolysis are identified as Fe(CO)2 and a product that is most likely Fe(CO).Both Fe(CO)2 and Fe(CO)3 are produced on 248-nm photolysis.Photolysis at 351 nm leads to the production of both Fe(CO)3 and Fe(CO)4.Species best assigned as excited states of Fe(CO)3 and Fe(CO)4 are observed to form as initial photoproducts following 248- and 351-nm photolysis, respectively.The magnitudes of the rate constants for reaction of the various coordinatively unsaturated metal carbonyls formed in this study with parent Fe(CO)5 or CO (summarized in Table I) are consistent with the hypothesis that spin-allowed reactions will be rapid while spin-disallowed reactions will be considerably slower.To provide further data in testing this hypothesis, the reaction of Fe(CO)4 with both O2 and H2 has been measured.
Gase-Phase Organometallic Catalysis: Kinetics and Mechanism of the Hydrogenation of Ethylene by Fe(CO)3(C2H4)2
Miller, Michael E.,Grant, Edward R.
, p. 7951 - 7960 (2007/10/02)
Inert homogeneous gas-phase mixtures of ethylene and hydrogen plus a catalytic amount of Fe(CO)5 are transformed into active ethylene hydrogenation systems upon irradiation by near-UV light from a pulsed nitrogen laser.Organometallic species present in the active catalytic mixture are identified and monitored by Fourier transform infrared spectroscopy.The catalyzed reaction is followed by gas chromatography, which provides a measure of ethylene and hydrogenated product concentrations.The catalytic process is efficient in its use of light, with typical room temperature quantum yields (product ethane molecules formed per photon absorbed) of 20 or more.The absorbed laser light generates a reservoir of Fe(CO)3(C2H4)2, which thermally dissociates by losing one highly labile ethylene to yield the active catalyst, Fe(CO)3(C2H4).When the photolysis light is removed, catalytic activity is observed to decline as the catalyst combines with free CO to form stable Fe(CO)4(C2H4).The rate of organic product formation is directly proportional to the catalyst reservoir concentration.Quantum efficiency of ethane production and the rate of Fe(CO)3(C2H4)2 decay are studied as functions of ethylene, hydrogen, CO, and Fe(CO)5 pressures.The results provide information on the mechanism of catalysis, as well as elementary rate parameters for many of the organometallic reactions.
Photochemical activation of molecular hydrogen by Fe(CO)5
Krusic, Paul J.,Jones, David J.,Christopher Roe
, p. 456 - 460 (2008/10/08)
The low-temperature photolysis of pentane solutions of Fe(CO)5 under various high pressures of molecular hydrogen or H2/CO mixtures has been investigated by ESR and NMR using a new sapphire high-pressure cell. The major diamagnetic products identified by proton NMR are the thermally unstable hydrides H2Fe(CO)4 and H2Fe2(CO)8, while the paramagnetic products identified by ESR are HFe(CO)4·, HFe2(CO)8·, HFe3(CO)11· and two paramagnetic trihydrides. Isotopic substitution studies with deuterium, 13C, and 57Fe were carried out to substantiate the assignments of these labile radical species and to obtain structural information.
Kinetic and Thermodynamic Acidity of Hydrido Transition-Metal Complexes. 3. Thermodynamic Acidity of Common Mononuclear Carbonyl Hydrides
Moore, Eric J.,Sullivan, Jeffrey M.,Norton, Jack R.
, p. 2257 - 2263 (2007/10/02)
The pKa values of the common mononuclear carbonyl hydrides have been determined in acetonitrile by IR measurement of the position of deprotonation equilibria with various nitrogen bases and potassium phenolate.The resulting values cover a range of about 20 pKa units, from 8.3 for HCo(CO)4 to 26.6 for CpW(CO)2(PMe3)H.Hydrides with η5-C5Me5 ligands are appreciably weaker acids than the corresponding hydrides with η5-C5H5 ligands (e.g., the pKa of (η5-C5Me5)Fe(CO)2H is 26.3, while that of (η5-C5H5)Fe(CO)2H is 19.4).The acidities of the group 8 carbonyl hydrides H2M(CO)4 decrease in the order Fe > Ru > Os.
Syntheses of iron carbonyl trimethylsilanes: Preparations and interconversions of cis-(CO)4Fe[Si(CH3)3]2, M+[(CO)4FeSi(CH3)3]-, and trans-[-Fe(CO)4Si(CH3)3]2
Blakeney, Andrew J.,Johnson, Dennis Lee,Donovan, Patrick W.,Gladysz
, p. 4415 - 4419 (2008/10/08)
Reaction of petroleum ether slurries of M2Fe(CO)4 (M = Na, K) with (CH3)3SiBr results in ca. 50% yields of cis-(CO)4Fe[Si(CH3)3]2 (1). When K2Fe(CO)4 is reacted with (CH3)3SiBr for 0.5 h in THF, fair yields of K+[(CO)4FeSi(CH3)3]- (2a) are obtained. Reaction of (CO)4Fe(H)Si(CH3)3 with KH and NaH affords 2a (90%) and Na+[(CO)4FeSi(CH3)3]- (2c; 68%), respectively. Both 2a and 2c are oxidized by C7H7+PF6- to the labile binuclear complex trans-[-Fe(CO)4Si(CH3)3]2 (3). Complex 3 can be independently generated from 1 and benzaldehyde and is reduced by Na/Hg to 2c. Other reactions and interconversions of these silanes are described. Some earlier unsuccessful attempts to prepare 1 by related routes are discussed.
