288394-53-6

Upstream product

• 1493-13-6 trifluorormethanesulfonic acid 
• 99038-25-2 [5,10,15,20-tetrakis(2,6-difluorophenyl)porphyrinate iron(III)] chloride 
• 2923-28-6 silver trifluoromethanesulfonate 
• 75-05-8 acetonitrile 

Relevant academic research and scientific papers

Hydroxylation of aliphatic hydrocarbons with m-chloroperbenzoic acid catalyzed by electron-deficient iron(III) porphyrin complexes

The catalytic hydroxylation of aliphatic hydrocarbons by m- chloroperbenzoic acid (MCPBA) has been studied in the presence of electron- deficient iron(III) porphyrin complexes. High yields of alcohol products were obtained with small amounts of ketone formation under mild reaction conditions. The stereospecificity and regioselectivity of the iron porphyrin complexes have been investigated in hydroxylation reactions as well. The hydroxylation of alkanes has been performed in the presence of isotopically 18O-labeled water, H218O, in order to understand the effects of the electronic nature of iron porphyrin complexes, the concentration of H218O, the C-H bond strength of alkanes, and the reaction temperature on the 18O- incorporation from the labeled water into alcohols. We found that the amounts of 18O incorporated into the alcohol products varied in the reactions; these results were interpreted with that the reaction of oxygen atom transfer from a high-valent iron oxoporphyrin complex to alkanes competes with that of oxygen atom exchange between the intermediate and labeled water that leads to 18O-incorporation from H218O into the alcohol products. Deuterium kinetic isotope effects (KIEs) in the alkane hydroxylations by the iron porphyrin complexes and MCPBA have been studied with a mixture of cyclohexane and cyclohexane-d12. The KIE values obtained in the reactions were found to depend significantly on the nature to the iron porphyrin complexes. The temperature dependence of k(H)/k(D) was also studied from -40 to 25 °C and the parameters of Arrhenius equation (i.e., the pre-exponential factor ratio, A(H)/A(D), and the isotopic difference of C-H and C-D bond activation energies, E(a)(D)-E(a)(H)) were determined.

Generation and characterization of [(P)M-(X)-CO(TMPA)]n+ assemblies; P = porphyrinate, M = FeIII and CoIII, X = O2-, OH-, O22-, and TMPA = tris(2-pyridylmethyl)amine

With the established chemistry of bridged [(porphyrinate)Fe III-X-CuII(ligand)]n+ [X = O2- (oxo), OH- (hydroxo), O22- (peroxo)] complexes, we investigated the effect of cobalt ion substitution for copper or copper and iron. Thus, in this report, the generation and characterization of new μ-oxo, μ-hydroxo, and μ-peroxo (μ-X) assemblies of [(porphyrinate)M III-X-CoII/III(TMPA)]n+- assemblies is described, where M = FeIII or CoIII and TMPA = tris(2-pyridylmethyl)amine. The μ-oxo complex [(F8TPP)Fe III-O-CoII(TMPA)]+ (1, F8TPP = tetrakis(2,6-difluorphenyl)-porphyrinate) was isolated by an acid-base self-assembly reaction of a 1:1 mixture of (F8TPP)FeIII-OH and [CoII(TMPA)(MeCN)]2+ upon addition of triethylamine. The crystal structure of 1·2C4H10O proved the presence of an unsupported Fe-O-Co moiety; ∠Fe-O-Co = 171.6° and d(Fe...Co) = 3.58 A. Complex 1 was further characterized by UV-vis (λmax = 437 (Soret) and 557 nm), 1H NMR [δ 40.6 (pyrrole-H), 8.8 and 8.7 (m-phenyl-H), 8.0 (p-phenyl-H), 4.4 (PY-4H), 2.6 (PY-3H), 1.0 (PY-5H), -1.1 (PY-6H), and -2.7 (TMPA-CH2-) ppm], electrospray ionization (ESI) and matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometric methods, Evans method NMR (μeff = 3.1), and superconducting quantum interference device (SQUID) susceptometry (J = -114 cm-1, S = 1). The μ-hydroxo analogue [(F8TPP)FeIII-(OH)-CoII(TMPA)] + (2) [UV-vis λmax = 567 nm; δ 78 ppm (pyrrole-H); Evans NMR μeff = 3.7] was generated by addition of 1 equiv of triflic acid to 1. The protonation is completely reversible, and 1 is regenerated from 2 by addition of triethylamine. While (F8TPP)Fe II/[CoII(TMPA)(MeCN)]2+/O2 chemistry does not lead to a stable μ-peroxo species, a dicobalt μ-peroxo complex [(TPP)CoIII(O22-)-CoIII(TMPA)] 2+ (3, TPP = meso-tetraphenylporphyrinate) forms from a reaction of O2 with a 1:1 mixture of the CoII precursor components at -80°C [UV-vis λmax = 435 (Soret), 548, and 583 (weak) nm; silent EPR spectrum; diamagnetic NMR spectrum]. The oxygenation/deoxygenation equilibrium is reversible; warming solutions of 3 releases ～1 equiv of O2 and the reduced complexes are reformed.

Reactivity studies on FeIII-(O22-)-Cu II compounds: Influence of the ligand architecture and copper ligand denticity

Heme-Cu/O2 adducts are of interest in the elucidation of the fundamental metal-O2 chemistry occurring in heme-Cu enzymes which effect reductive O-O cleavage of dioxygen to water. In this report, the chemistry of four heme-peroxo-copper [FeIII-(O2 2-)-CuII]+ complexes (1-4), varying in their ligand architecture, copper-ligand denticity, or both and thus their structures and physical properties are compared in their reactivity toward CO, PPh 3, acids, cobaltocene, and phenols. In 1 and 2, the copper(II) ligand is N4-tetradentate, and the peroxo unit is bound side-on to iron(III) and end-on to the copper(II). In contrast, 3 and 4 contain a N 3-tridentate copper(II) ligand, and the peroxo unit is bound side-on to both metal ions. CO displaces the peroxo ligand from 2-4 to form reduced CO-FeII and CO-CuI species. PPh3 reacts with 3 and 4 displacing the peroxide ligand from copper, forming (porphyrinate)FeIII-superoxide plus CuI-PPh3 species. Complex 2 does not react with PPh3, and surprisingly, 1 reacts neither with PPh3 nor CO, exhibiting remarkable stability toward these reagents. The behavior of 1 and 2 compared to that of 3 and 4 correlates with the different denticity of the copper ligand (tetra vs tridentate). Complexes 1-4 react with HCl releasing H2O2, demonstrating the basic character of the peroxide ligand. Cobaltocene causes the two-electron reduction of 1-4 giving the corresponding μ-oxo [Fe III-(O2-)-CuII]+ complexes, in contrast to the findings for other heme-peroxo-copper species of different design. With t-butyl-substituted phenols, no reaction occurs with 1-4. The results described here emphasize how ligand design and variations influence and control not only the structure and physical properties but also the reactivity patterns for heme-Cu/O2 adducts. Implications for future investigations of protonated heme/Cu-peroxo complexes, low-spin analogues, and ultimately O-O cleavage chemistry are discussed.