21255-52-7

Upstream product

• 17685-52-8 triiron dodecarbonyl 
• 603-35-0 triphenylphosphine 
• 13463-40-6 iron pentacarbonyl 
• 14264-16-5 bis(triphenylphosphine)nickel(II) chloride 
• 107514-04-5 Na{Fe(CO)3(PPh₃)(SiMePh₂)} 
• 12120-15-9 ethylenebis(triphenylphosphine)platinum⁽⁰⁾ 
• 53765-62-1 {(CO)2Fe(P(C₆H₅)3)2N₂C₆H₄CH₃-p}BF₄ 
• 201230-82-2 carbon monoxide 
• 124-41-4 sodium methylate 
• 15530-61-7 FeI₂(CO)₃PPh₃ 
• 107514-06-7 K⁽¹⁺⁾*{Fe(CO)3(P(C₆H₅)3)(Si(OCH₂CH₃)3)}^(1-)=K{Fe(CO)3(P(C₆H₅)3)(Si(OCH₂CH₃)3)} 
• 137038-33-6 {Fe(CO)3(P(C₆H₅)3)2}⁽¹⁺⁾ 
• 74242-48-1 tricarbonyl[(1-4-η)-2-methoxycyclohexa-1,3-diene]iron 
• 64424-68-6 [Fe(CO)2(PPh3)2(η2-CS2)] 

Downstream Products

• 110455-81-7 iron(carbonyl)3((phenyl)3phosphine)Br₂ 
• 110507-75-0 iron(II)(carbonyl)2((phenyl)3phosphine)2Cl₂ 
• 137038-33-6 {Fe(CO)3(P(C₆H₅)3)2}⁽¹⁺⁾ 
• 35679-07-3 tetracarbonyl(triphenylphosphine)iron 
• 19601-47-9 (CO)3FeP(C₆H₅)3ClSnCl₃ 
• 212395-29-4 Fe(COOCH₃)(CO)4(P(C₆H₅)3)⁽¹⁺⁾*BF₄^(1-)=[Fe(COOCH₃)(CO)4(P(C₆H₅)3)]BF₄ 

Relevant academic research and scientific papers

Olefin replacement on cyclooctatetraeneiron tricarbonyl by neutral ligands

Kinetic data are reported on reactions of cyclooctatetraeneiron tricarbonyl with tertiary phosphines (L) and 1,2-bis(diphenylphosphino)ethane (L-L) in decalin at various temperatures. The reactions involve replacement of cyclooctatetraene leading to trans-Fe(CO)3L2 and cis-Fe(CO)3(L-L). Reaction rates depend on the nature and concentration of the entering ligand. Results are interpreted in terms of a mechanism consisting of a slow coordination of L on the substrate followed by fast elimination of cyclooctatetraene from the resulting labile intermediate. Activation parameters are discussed to support this mechanism.

Heterometallic Cu2Fe and Zn2Fe2Complexes Derived from [Fe(CO)4]2-and Cu/Fe Bifunctional N2O Activation Reactivity

The synthesis and characterization of two heterometallic clusters, [(IPr)Cu]2Fe(CO)4 (1) and [(IPr)ZnFe(CO)4]2 (2), derived from Collman's reagent are reported. Methylation of 1 with CH3I to produce (IPr)CuI and (IPr)CuFe(Me)(CO)4 (3) was used to calibrate the relative reactivity of 1 to the previously studied analogue (IPr)Cu-FeCp(CO)2. Bifunctional N2O activation by 1 resulted in oxidation of a CO ligand to carbonate rather than the more typically observed CO2, producing [(IPr)Cu]2(μ-CO3) (4) stoichiometrically along with an iron byproduct that was trapped with PPh3 as trans-Fe(CO)3(PPh3)2.

Iron pentacarbonyl in alkoxy- and aminocarbonylation of aromatic halides

We have identified reaction conditions for a Heck-type carbonylation based on [Fe(CO)5]. Preliminary optimization of alkoxycarbonylation on 2-bromonaphthalene defined functioning composition of the reaction mixture which was then applied on a small set of (hetero)aromatic halides. Respective aminocarbonylation of these halides with different amines, including aniline and benzotriazole, was accomplished with reasonable results.

Light-enhanced displacement of methyl acrylate from iron carbonyl: Investigation of the reactive intermediate via rapid-scan fourier transform infrared and computational studies

The thermal displacement of methyl acrylate from Fe(CO)4(η 2-CH2=CHCOOMe) by phosphine ligands is a relatively slow reaction requiring several hours at elevated temperatures. In the present study, it is observed that photolysis of the tetracarbonyl complex with UV light activates the process such that the reaction is complete within a few seconds. This rate enhancement is due to the formation of an intermediate η4 complex where the organic C=O and C=C units of methyl acrylate occupy axial and equatorial coordination sites on the Fe center, respectively, following photochemical CO loss. The displacement of methyl acrylate from this photolytically generated intermediate is facile with a remarkably low barrier of 8.7 kcal/mol. Density functional theory calculations support these experimental observations.

Acrylic acid derivatives of group 8 metal carbonyls: A structural and kinetic study

The synthesis, spectroscopic, and X-ray structural studies of acrylic acid complexes of iron and ruthenium tetracarbonyls are reported. In addition, the deprotonated η2-olefin bound acrylic acid derivative of iron as well as its alkylated species were fully characterized by X-ray crystallography. Kinetic data were determined for the replacement of acrylic acid, acrylate, and methylacrylate for the group 8 metal carbonyls by triphenylphosphine. These processes were found to be first-order in the concentration of metal complex with the rates for dissociative loss of the olefinic ligands from ruthenium being much faster than their iron analogues. However, the ruthenium derivatives afforded formation of primarily mono-phosphine metal tetracarbonyls, whereas the iron complexes led largely to trans-di-phosphine tricarbonyls. This difference in behavior was ascribed to a more stable spin crossover species 3Fe(CO)4 which undergoes rapid CO loss to afford the bis phosphine derivative. The activation enthalpies for dissociative loss of the deprotonated η2-bound acrylic acid ligand were found to be larger than their corresponding values in the protonated derivatives. For example, for dissociative loss of the protonated and deprotonated acrylic acid derivatives of iron(0) the ΔH? values determined were 28.0 ± 1.2 and 34.1 ± 1.5 kcal·mol-1, respectively. Density functional theory (DFT) computations of the bond dissociation energies (BDEs) in these acrylic acids and closely related complexes were in good agreement with enthalpies of activation for these ligand substitution reactions, supportive of a dissociative mechanism for olefin displacement. Processes related to catalytic production of acrylic acid from CO2 and ethylene are considered.

Iron-catalyzed hydrogen production from formic acid

Hydrogen represents a clean energy source, which can be efficiently used in fuel cells generating electricity with water as the only byproduct. However, hydrogen generation from renewables under mild conditions and efficient hydrogen storage in a safe and reversible manner constitute important challenges. In this respect formic acid (HCO2H) represents a convenient hydrogen storage material, because it is one of the major products from biomass and can undergo selective decomposition to hydrogen and carbon dioxide in the presence of suitable catalysts. Here, the first light-driven iron-based catalytic system for hydrogen generation from formic acid is reported. By application of a catalyst formed in situ from inexpensive Fe3(CO)12, 2,2′:6′2′′-terpyridine or 1,10-phenanthroline, and triphenylphosphine, hydrogen generation is possible under visible light irradiation and ambient temperature. Depending on the kind of N-ligands significant catalyst turnover numbers (>100) and turnover frequencies (up to 200 h-1) are observed, which are the highest known to date for nonprecious metal catalyzed hydrogen generation from formic acid. NMR, IR studies, and DFT calculations of iron complexes, which are formed under reaction conditions, confirm that PPh3 plays an active role in the catalytic cycle and that N-ligands enhance the stability of the system. It is shown that the reaction mechanism includes iron hydride species which are generated exclusively under irradiation with visible light.

Microwave synthesis of benchmark organo-iron complexes

Microwave-assisted reaction techniques have been applied to the formation of a variety of organo-iron species. The species synthesized include ferrocene and acetyferrocene, piano stool complexes such as CpFe(CO)2I, CpFe(PPh3)(CO)I, a

Phosphine addition to pyruvoyl ligands of iron complexes: Formation of zwitterionic metallalactones

Tertiary phosphines react, at -80 °C, with the pyruvoyl-substituted iron complex (CO)4Fe[C(O)C(O)CH3](CO2CH 3) (1) to give rise to phosphonium-substituted metallalactones fac-(CO)3e[C(O)C(CH3/su

Novel thermolytic products and their structures derived from thermolysis of isomerized products of spiro[4.4]nona-1,3-diene(dicarbonyl)[ethoxy(aryl)carbene]iron phosphine adducts [(η3-C9H12)Fe{C(OC2H5)Ar}(CO)2PPh3]

Heating a benzene solution of the isomerized product of spiro[4.4]nona-1,3-diene(dicarbonyl)[ethoxy(aryl)carbene]iron phosphine adduct [(η3-C9H12)Fe{C(OC2H5)(C6H4CH3-o)}(CO)2PPh3] (1) in a sealed quartz tube at 85-90 °C for 72 h gave the ring-opened η4 olefin-coordinated dicarbonyliron phosphine complex [Fe{η4-C5H7CH{double bond, long}CHCH2CH{double bond, long}C(OC2H5)C6H4CH3-o}(CO)2PPh3] (3) and cyclobutane derivative [C24H22O7] (4). The thermal decomposition of analogous isomerized product [(η3-C9H12)Fe{C(OC2H5)(C6H4CH3-p)}-(CO)2PPh3] (2) afforded the corresponding η4 olefin-coordinated dicarbonyliron phosphine complex [Fe{η4-C5H7CH{double bond, long}CHCH2CH{double bond, long}C(OC2H5)C6H4CH3-p}(CO)2PPh3] (6) and compound 4. The structures of products 3 and 4 have been established by X-ray diffraction studies.

Proton sponge phosphines: Electrospray-active ligands

Attachment of a proton sponge to a phosphine ligand renders neutral complexes of the ligand highly amenable to analysis by electrospray ionisation mass spectrometry (ESI-MS). The ligand 1,8-bis(dimethylamino) naphthyldiphenylphosphine (3) is extremely eff