82540-99-6

Upstream product

• 17685-52-8 triiron dodecarbonyl 
• 25879-01-0 {Et₄N}{(H)tetracarbonyl iron} 
• 92055-46-4 {((C₆H₅)3P)2N}⁽¹⁺⁾*{HFe₃(CO)9BH₃}^(1-)={((C₆H₅)3P)2N}{HFe₃(CO)9BH₃} 
• 89322-19-0 ((C₆H₅)3P)2N⁽¹⁺⁾*Fe₃Ni(CO)12H^(1-)=(((C₆H₅)3P)2N)(Fe₃Ni(CO)12H) 

Downstream Products

• 100447-70-9 Fe₃(CO)12 

Relevant academic research and scientific papers

Synthesis of [AsPh4][Fe3(CO)9(μ-CO)(μ 3-HBCl)] by oxidative chloride substitution of [Fe3(CO)9(μ3-HBCO)]2-

The deprotonation of (μ-H)Fe3(CO)9(μ-CO)(μ3-HBH) with n-butyllithium yields the dianionic complex [Li]2[Fe3(CO)9(μ3-HBCO)], which has been spectroscopically characterized. In contrast to the facile reprotonation of closely related ferraboranes, protonation of [Li]2[Fe3(CO)9(μ3-HBCO)] leads to decomposition. On the other hand, reaction of this dianionic complex with 2 equiv of FeCl3 gives a good yield of [Li][Fe3(CO)9(μ-CO)(μ3-HBCl). Metathesis with [AsPh4][Cl] yields [AsPh4][Fe3(CO)9(μ-CO)(μ 3-HBCl)], which has been crystallographically characterized (triclinic, P1, a = 9.534(3) A?, b = 13.305(4) A?, c = 15.225(4) A?, α = 104.39(2)°, β = 103.56(2)°, γ = 99.23(2)°, V = 1768.7(8) A?3, Z = 2). Comparison with the analogous osmium clusters, as well as isoelectronic organometallic clusters, reveals relationships among their structures, properties, and energetics.

Electron Transfer Catalysis in the Conversion of Fe3(CO)12 to Fe(CO)5

Evidence strongly suggests that the reaction Fe(CO)12 with CO yield Fe(CO)5 occurs via an electron transfer catalysed pathway; a mechanism for the reaction is proposed.

Main Group Chemistry on a Metal Framework: Reactions of - (R=H, CH3) with Lewis Bases

The reactions of - (R=H, CH3) with Lewis bases (L=CO, PhMe2P, NEt3, and H2O) are explored.For R=H and L=PhMe2P, substitution via H2 rather than CO elimination to yield -, Fe(CO)3(PhMe2P)2, and a ferroborane anion spectroscopically characterized in situ.The fragmentation pathway predominates in the presence of excess Lewis base, whereas H2 elimination is favored by low ligand levels.For L=PhMe2P the H2 displacement pathway is promoted with R=CH3.A kinetic study for L=PhMe2P reveals a first-order rate dependence on both substrate and ligand for fragmentation, suggesting associative activation.The dual-fragmentation path observed illustrates competitive base displacement of isoglobal fragments from a single cluster.An analysis at intermediate ligand levels results in the definition of base-promoted cluster substitution via H2 elimination.Under the conditions explored here, CO yields only H2 displacement, H2O only fragmentation, and NEt3 adduct formation with slow fragmentation but no H2 displacement.

Kinetics and mechanism of the reaction of [Et4N][HFe(CO)4] and alkyl halides. The unexpected formation of acetone

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.

Synthesis of bimetallic Fe-Ni carbonyl clusters: Crystal structure of [N(CH3)3CH2Ph][Fe3Ni(CO) 8(μ-CO)4(μ3-H)]

Redox condensation of [Fe3(CO)11]2- with Ni(CO)4 in tetrahydrofuran affords the tetranuclear dianion [Fe3Ni(CO)12]2-. Subsequent protonation with acids results in formation of the corresponding [Fe3Ni(CO)12H]- anion. This monoanionic species has also been obtained by reaction of [Fe3(CO)11]2- with NiCl2·xEtOH. Both Fe3Ni systems have been isolated in the solid state in high yield with a variety of tetrasubstituted ammonium and phosphonium salts. An X-ray diffraction study of the trimethylbenzylammonium salt of [Fe3Ni(CO)12H]- reveals a structure with a tetrahedron of metal atoms surrounded by eight terminal and four edge-bridging carbonyl groups. The hydride ligand has been located over the center of an Fe2Ni face at a distance of 0.60 (3) A? from the trimetal plane. The corresponding [Fe3Ni(CO)12]2- dianion is suggested to posses an analogous structure on the basis of its IR spectrum. Crystallographic data for [C10H16N]+[C12HFe 3NiO12]-: fw 713.64, triclinic, space group P1, Z = 2, a = 7.416 (1) A?, b = 13.849 (2) A?, c = 14.108 (2) A?, α = 103.13 (2)°, β = 103.15 (2)°, γ = 99.23 (2)°, R(F2) = 0.030 for 3860 reflections measured at room temperature.