71564-23-3Relevant academic research and scientific papers
Chain-ring isomerism vs. carbon-carbon coupling on two (tetracarbonyliron)-γ-ketoesters: Cis-[Fe(COR)(COCOR′)(CO)4] (R = Me, R′ = OMe; R = OMe, R′ = Me)
Sellin, Murielle,Luart, Denis,Salauen, Jean-Yves,Laurent, Pascale,Toupet, Loic,Des Abbayes, Herve
, p. 857 - 858 (1996)
Ferra-γ-ketoesters 1 and 2 induce thermally either a carbon-carbon coupling process or a chain-ring isomerization; the orientation of the reaction likely depends on the proximity of the ester group to the metal centre.
Oxidative addition of thioesters to iron(0): active-site models for Hmd, nature's third hydrogenase
Royer, Aaron M.,Rauchfuss, Thomas B.,Gray, Danielle L.
, p. 3618 - 3620 (2009/12/08)
The thioester Ph2PC6H4-2-C (O ) SPh reacts with Fe2(CO)9 to give [Ph2PC6H 4C(O)]Fe(SPh) (CO)3, a model for the CO-inhibited active site of the enzyme Hmd. T
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 (2007/10/03)
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.
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 (2008/10/09)
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
Low-valent α-diimine iron complexes for catalytic olefin hydrogenation
Bart, Suzanne C.,Hawrelak, Eric J.,Lobkovsky, Emil,Chirik, Paul J.
, p. 5518 - 5527 (2008/10/09)
A family of low-valent α-diimine iron complexes has been synthesized and their utility in catalytic olefin hydrogenation reactions evaluated. Reduction of the ferrous dichloride complex [ArN=C(Me)C(Me)=NAr]FeCl2 (Ar = 2,6-(CHMe2)2-C6H3) with sodium amalgam in benzene or toluene furnished the iron arene complexes, [ArN=C(Me)C(Me)=NAr]Fe(η6-C6H5R) (R = H, Me). The solid-state structure of the toluene adduct revealed a contracted carbon-carbon backbone, short iron-imine bonds, and elongated imine nitrogen-carbon distances, suggesting significant reduction of the α-diimine ligand. The analogous reduction in alkane solvents afforded the bis(α-diimine) complex [ArN=C(Me)C(Me)=NAr]2Fe, which has also been crystallographically characterized. The arene complexes and the bis(a-diimine) complexes are inactive for catalytic olefin hydrogenation. Performing the reduction in the presence of internal alkynes such as diphenylacetylene and bis(trimethylsilyl)acetylene furnished the alkyne adducts [ArN=C(Me)C(Me)=NAr]Fe(η2-RC=CR) (R = Ph, SiMe3 ). Analogous olefin complexes with 1,5-cyclooctadiene and cycloctene have also been isolated using similar reduction procedures. The olefin adducts provide more active precatalysts than the alkyne compounds for the hydrogenation of 1-hexene. In each case, formation of rfarene adducts serves as a major catalyst deactivation pathway.
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 (2008/10/08)
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.
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 (2007/10/03)
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.
Kinetics and mechanism of the reaction of [Et4N][HFe(CO)4] and alkyl halides. The unexpected formation of acetone
Whitmire, Kenton H.,Lee, T. Randall,Lewis
, p. 987 - 994 (2008/10/08)
When [Et4N][HFe(CO)4] is treated with methyl iodide in CH3CN at 25.0 ± 0.2°C, a clean second-order reaction ensues as monitored via the change in the intensity of νCO of the metal carbonyl hydride. In all cases, yields of CH4 were 85-100%. A second-order rate constant (first order in iron and in CH3I) of (1.7 ± 0.1) × 10-2 M-1 s-1 was determined, and activation parameters of Ea = 11.2 ± 1.0 kcal/mol, ΔH? = 10.6 ± 1.0 kcal/mol, and ΔS? = -33 cal/(mol K) were found over the temperature range 15-35°C. The iron product from this reaction is thought to be the unstable Fe(CO)4(NCCH3) , which can also be generated from Fe(CO)5 in CH3CN by irradiation or use of (CH3)3NO. Reaction of iron hydride with 6-bromo-1-hexene produced only 1-hexene and no detectable methylcyclopentane. Reaction with cyclopropylcarbinyl bromide yielded primarily methylcyclopropane and lesser amounts of 1-butene and cis- and trans-2-butene, although evidence is presented to suggest nonrigorously that this is a side reaction. A simple nucleophilic substitution is proposed as the rate-determining step. During this study acetone was detected and confirmed as a reaction product by isotope-labeling studies. A mechanism for this latter observation is discussed.
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 (2007/10/02)
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.
Evidence for intramolecular pathways in C-C bond-forming reactions proceeding from binuclear iron complexes
Sundararajan, Govindarajan,San Filippo Jr., Joseph
, p. 606 - 608 (2008/10/08)
Decomposition of the binuclear iron complex 2 (R = n-C9H19) in THF or cyclohexane yields three products: n-octadecane, 10-nonadecanone, and 10,11-eicosodione. The principal organometallic product is Fe-(CO)5. Decomposition obeys first-order kinetics and is characterized by an unusually large, negative entropy of activation, ΔS ? = -29 cal/(mol K) (log A = 6.07). The failure to observe any crossover products demonstrates that these decomposition products are produced in processes which do not involve alkyl group scrambling and presumably occur by intramolecular pathways. The reactivity of 2 with methyl iodide and triphenylphosphine has also been briefly examined.
