52253-91-5

Upstream product

• 13463-40-6 iron pentacarbonyl 
• 672-66-2 Dimethyl(phenyl)phosphine 
• 98814-91-6 Fe2(CO)6(μ-COEt)(μ-CHCH2) 
• 92055-46-4 {((C₆H₅)3P)2N}⁽¹⁺⁾*{HFe₃(CO)9BH₃}^(1-)={((C₆H₅)3P)2N}{HFe₃(CO)9BH₃} 
• 17685-52-8 triiron dodecarbonyl 
• 122-57-6 1-Phenylbut-1-en-3-one 
• 39114-08-4 2,2,2,2-tetracarbonyl-1,1-dimethyl-1-sila-2-ferracyclopentane 
• 15616-56-5 diiodotetracarbonyliron(II) 
• 38720-22-8 (2-methyl-4-phenyl-1-oxabuta-1,3-diene)tricarbonyliron⁽⁰⁾ 
• 17857-24-8 tetracarbonylhydridoferrate 

Downstream Products

• 25226-45-3 (CO)2Fe(P(CH₃)2C₆H₅)2I₂ 
• 32876-93-0 C₉F₁₂OFe(CO)2P(CH₃)2C₆H₅ 
• 136706-70-2 {Fe(H)(CO)3(P(CH₃)2C₆H₅)2}⁽¹⁺⁾*CF₃SO₃^(1-)={Fe(H)(CO)3(P(CH₃)2C₆H₅)2}CF₃SO₃ 

Relevant academic research and scientific papers

Enthalpies of reaction of (benzylideneacetone)iron tricarbonyl, (BDA)Fe(CO)3, with phosphine ligands. Thermodynamic insights into iron chemistry

The enthalpies of reaction of (BDA)Fe(CO)3 (BDA = benzylideneacetone) with a series of monodentate phosphine ligands (PR3) leading to the formation of trans-(PR3)2Fe(CO)3 complexes have been measured by solution calorimetry in THF at 50°C. These enthalpy data help establish the following relative order of stability: PEt3 > PnBu3 > PMe3 > PPhMe2 > PPh2Me > PPh3. The data span a range of 15 kcal/mol. This stability scale sheds light on the relative donating ability of phosphines. These data also allow comparison with other organometallic systems and give insight into factors influencing the Fe-PR3 bond disruption enthalpies in the (PR3)2Fe-(CO)3 system.

SYNTHESIS, CHARACTERIZATION AND REACTIVITY OF BROMO(syn-η3-2,4-PENTADIENYL)TRICARBONYLIRON

The reaction between trans-1-bromopenta-2,4-diene and nonacarbonyldiiron in pentane yields (syn-η3-C5H7)Fe(CO)3Br.The spectroscopic data and chemical reactivities of this compound are reported and discussed.

Reductive elimination of halogens assisted by phosphine ligands in Fe(CO)4X2 (X = I, Br) complexes

Fe(CO)4X2 complexes [X = I (1), Br(1′)] react with phosphine ligands L (L = PMe3, PEt3, PMe2Ph, PMePh2, PPh3) via a two-step mechanism: in the first step fac-Fe(CO)3LX2 complexes are formed; in the second step two parallel pathways, a and b, are observed; in pathway a, reductive elimination with formation of equimolar amounts of Fe(CO)3L2 (5) and phosphonium salts [LX]+X- is observed; in pathway b, disubstituted dihalide complexes cis,trans,cis-Fe(CO)2L2X2 are formed. The relative weights of pathways a and b depend on the basicity, steric hindrance and concentration of ligand L, on the nature of the halogen and on temperature. A radical mechanism which accounts for most of the experimental results is proposed.

Enthalpies of reaction of (diene)- and (enone)iron tricarbonyl complexes with monodentate and bidentate ligands. Solution thermochemical study of ligand substitution in the L2Fe(CO)3 complexes

The enthalpies of reaction of (BDA)Fe(CO)3 (BDA = (C6H5)CH=CHO(CH3), benzylideneacetone) with a series of mono- and multidentate ligands, leading to the formation of (η4-L)Fe(CO)3, (L′)2Fe(CO)3, and (L″)Fe(CO)3 complexes (L = diene, enone; L′ = monodentate arsines; L″ = bidentate ligands), have been measured by solution calorimetry in THF at 50°C. The range of reaction enthalpies spans some 44 kcal/mol. The overall relative order of stability established is as follows: for monodetate ligands, AsPh3 3 a relative order of complex stability for these compounds in the iron tricarbonyl system. These data allow the calculation of the enthalpy associated with the geometric isomerization process (axial-equatorial/ diaxial) present in the (L′)2Fe(CO)3 system (5.4 ± 0.5 kcal/mol) as well as for a quantitative analysis of ring strain energies in the (L″)Fe(CO)3 system. The four-membered metallacycle is the only cyclic structure exhibiting significant strain energy (12.6 kcal/mol). Comparisons with other organometallic systems and insight into factors influencing the Fe-L bond disruption enthalpies are also discussed.

Ligand substitution processes on carbonylmetal derivatives. 1. Reaction of tetracarbonylhydridoferrates with phosphines

Ligand substitution processes on KHFe(CO)4 (1) have been demonstrated for the first time by reaction with various phosphines (2 equiv). The reaction times and the nature of the reaction products strongly depend on (i) the nature of the solvent, (ii) the cone angle of the phosphine, and (iii) the reaction conditions. In protic media (e.g. EtOH), phosphines with small cone angles (P(n-Bu)3, PMe2Ph) react with 1 below room temperature to give the newly characterized H2Fe(CO)2(PR3)2 in good yield, whereas phosphines with larger cone angles react only at higher temperature and afford the disubstituted Fe(CO)3(PR3)2 derivatives in quantitative yield. In aprotic medium (THF), phosphines (P(n-Bu)3, PPh3) react only slowly with 1 at room temperature but do so at reflux temperature to yield K2Fe(CO)4 (50%) and bis- or tris-(phosphine)carbonyliron derivatives. The reaction mechanism involves the formation of a monosubstituted K+[HFe(CO)3(PR3)]- derivative with a rate strongly dependent on the Tolman cone angle of the phosphine. In THF, this basic hydrido carbonyl anion reacts with 1 to yield K2Fe(CO)4 and H2Fe(CO)3(PR3). The latter further reacts to give bis- or tris(phosphine)carbonyliron derivatives. In ethanol, the monosubstituted K+[HFe(CO)3(PR3)]- derivative is protonated to give the neutral dihydride H2Fe(CO)3(PR3), which depending on the reaction conditions, is converted either to H2Fe(CO)2(PR3)2 by CO substitution (at low temperature) or to Fe(CO)3(PR3)2 by H2 elimination (at higher temperature). For phosphines exhibiting small cone angles, the disubstituted dihydride may react further with an excess of phosphine to yield the trisubstituted Fe(CO)2(PR3)3 derivative in good yield.

Use of BF4 to prepare thiolate complexes of iron and ruthenium

The complexes BF4 (L = PPh2Me, PPhMe2 P(OMe)3), 3SMe>BF4, and BF4 were prepared by reactions of BF4 and the appropriate neutral M(CO)5-n(L)n precursor.Several other analogous reactions were unsu

Heats of protonation of transition-metal complexes: The effect of phosphine basicity on metal basicity in CpIr(CO)(PR3) and Fe(CO)3(PR3)2

Titration calorimetry has been used to determine the effects of phosphine ligand basicity on the heats of protonation (ΔHHM) of the metal in the CpIr(CO)(PR3) and Fe(CO)3(PR3)2complexes (PR3/sub

Uebergangsmetall-Silyl-Komplexe. XL. Umsetzung von cis-Fe(CO)4(SiCl3-nMen)2 (n = 1-3) mit Phosphinene: Konkurrenz von CO-Substitution, SiR3-Abspaltung und Bildung zweikerniger, SiR2-verbrueckter Komplexe

Upon reaction of benzene solutions of the bissilyl complexes cis-Fe(CO)4(SiCl3-nMen)2 (n = 1-3) with triphenylphosphine no disilane elimination takes places.Instead, formation of phosphine-substituted bissilyl or hydrido silyl complexes, disiloxanes and F

Carbon-carbon bond formation at a diiron center. 5. Versatile action of phosphines on Fe2(CO)6(μ-COEt)(μ-CRCR′H) complexes (R = R′ = Ph, H)

The reaction of Fe2(CO)6(μ-COEt) (μ-CRCR′H) complexes (R = R′ = Ph, H) with the phosphines PPh3 and PMe2Ph is dependent on both phosphine and R. In the case where R = R′ = Ph, reaction with PPh3 leads only to the formation of Fe(CO)3(PPh3)2 in boiling hexane. With PMe2Ph the reaction occurs with CO substitution to give Fe2(CO)5(PMe2Ph)(μ-CPhCPhC(OEt)H) (3), in which the organic fragment is η1:η3 bound through the carbons to the two iron atoms and η1(O) bound through oxygen of the ethoxy group to an iron atom. In the case where R = R′ = H, reaction with PMe2Ph leads to the formation of Fe-(CO)5-n(PMe2Ph)n (n = 1, 2) in boiling hexane. With PPh3, coupling of the two organic bridges is observed and the reaction occurs without CO loss, leading to Fe2(CO)6(PPh3)(μ-C(OEt)CHCH2) (5). Protonation of 5 with HBF4·Et2O gives [Fe2(CO)7(PPh3)(μ-C(OEt)CH(Me))][BF 4], the structure of which has been established by an X-ray structure determination: triclinic; space group P1; a = 12.305 (1) A?, b = 16.069 (2) A?, c = 8.210 (1) A?; α = 95.61 (1)°, β = 90.35 (1)°, γ = 87.10 (1)°; Z = 2. The structure was solved and refined to R and Rw values of 0.031 and 0.032, respectively, with use of 3226 reflections.

Preparation and characterization by 31P-NMR spectroscopy of mixed disubstituted complexes

The disubstituted complexes , where L and L' are different phosphine ligands have been prepared by reaction of the hydrosilyl derivatives with L'.Good results were obtained for L = PMe3 and L' = PPh3, P(OPh)3, P(OEt)3 or P(O-i-Pr)3 but with L' = PMe2Ph, PMePh2, PEt3, a mixture of homo and mixed disubstituted derivatives were obtained.The results can be interpreted in terms of exchange of the L ligand in 3 with L'.The variations in the 31P NMR chemical shifts and 2JPP coupling constants are discussed in the light of the properties of the ligands, and good correlations are revealed with the cone angle and the pKa, respectively.