27882-93-5

Upstream product

• 677343-52-1 C₈₈H₁₆Cu₂F₄₀N₈ 
• 80937-33-3 oxygen 
• 142-71-2 copper diacetate 
• 25440-14-6 tetrakis(pentafluorophenyl)porphyrin 
• 72076-08-5 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin zinc(II) 
• 6046-93-1 copper(II) acetate monohydrate 
• 10294-33-4 boron tribromide 
• 10294-34-5 boron trichloride 
• 677343-52-1 Cu₂(([36]octaphyrin(1.1.1.1.1.1.1.1))(-4H)) 
• 155640-85-0 bis(1,1,1,5,5,5-hexafluoropentane-2,4,-dionato)copper(II)hydrate 

Downstream Products

• 173862-25-4 2-nitro-5,10,15,20-tetrakis(pentafluorophenylporphyrinato)copper(II) 
• 1448358-61-9 [5,10,15,20-tetra(pentafluorophenyl)porpholactone]Cu(II) 

Relevant academic research and scientific papers

Kinetics and mechanism for the metalation of 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin with bis(β-diketonato)copper(II) complexes in supercritical carbon dioxide and n-hexane

The copper(II) ion incorporation reactions into 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin (H2tpfpp) to form the Cu(tpfpp) complex have been kinetically investigated with bis-(β-diketonato)copper(II) complexes (CuL2) such as bis(1,1,1,5,5,5-hexafluoropentane-2,4-dionato)copper(II) (Cu(hfac)2), bis(1,1,1-trifluoropentane-2,4-dionato)copper(II) (Cu(tfac)2), bis(2,2,6,6-tetramethylheptane-3-5-dionato)copper(II) (Cu(hmac)2), and bis-(pentane-2,4-dionato)copper(II) (Cu(acac)2) in supercritical carbon dioxide (scCO2) using a previously developed stopped-flow instrument and spectrophotometric cell. Saturation dependence was observed for the conditional first-order rate constants (kobs) as a function of the mole fraction of excess CuL2 (xCu): kobs = k2K1xCu / (1 + K1xCu), where K1 is the preequilibrium constant for the fast outer sphere association between H2tpfpp and CuL2 and k2 is the first-order rate constant for the rate-determining copper(II) ion incorporation into the porphyrin core. Under constant temperature (333 K) and pressure (20.0 MPa), the K1 values are in the order of Cu(hfac)2 2 2 2: this trend has been interpreted by the differences in the solvation energy of the CuL2 complexes in scCO2 and in the electrostatic repulsion between H2tpfpp and CuL2 anticipated in the outer sphere association complex. On the other hand, the k2 values are in the following order: Cu(hfac)2 > Cu(tfac)2 > Cu(hmac)2 > Cu(acac)2. This order may be explained by the affinity of CuL2 the nucleophile of the pyrrolenine nitrogen, the easiness of dissociation of the β-diketonate ligand, and the electrostatic repulsion between H2tpfpp and CuL2. The thermodynamic and kinetic parameters in scCO2 were obtained as follows: K1 = (5.2 ± 0.1) × 104 (333 K, 20.0 MPa), ΔH1° = 76 ± 2 kJ mol-1 (20.0 MPa), ΔS1° = (3.2 ± 0.7) × 102 J mol1 K-1 (20.0 MPa), ΔV1° = (7.9 ± 0.6) × 102 cm3 mol-1 (333 K), k2 = (2.7 ± 0.3) × 10-4 s-1 (333 K, 20.0 MPa), Δ?H2° = -49 ± 9 kJ mol-1 (20.0 MPa), Δ?S2° = (-4.6 ± 0.3) × 102 J mol-1 K-1 (20.0 MPa), and Δ?V2° = (-4.4 ± 0.6) × 102 cm3 mol-1 (333 K). In addition, the reaction of H2tpfpp with Cu(hfac)2 has been studied in n-hexane in order to compare the results in scCO2 with those in a conventional nonpolar solvent.

Galactodendritic porphyrinic conjugates as new biomimetic catalysts for oxidation reactions

This work employed [5,10,15,20-tetrakis(pentafluorophenyl)porphyrin] ([H2(TPPF20)], H2P1) as the platform to prepare a tetrasubstituted galactodendritic conjugate porphyrin (H2P3). After metalation with excess c

Porphyrins. 40. Electronic spectra and four-orbital energies of free-base, zinc, copper, and palladium tetrakis(perfluorophenyl)porphyrins

Absorption and emission spectra and emission quantum yields are given for free-base (H2), Zn, Cu, and Pd derivatives of tetrakis(perfluorophenyl)porphyrin (TFPP). The four-orbital model is used to rationalize differences in the optical properties among the derivatives of TFPP and the same derivatives of porphine (P), octaethylporphyrin (OEP), and tetraphenylporphyrin (TPP). It is concluded from absorption data that the energy difference between the two excited singlets, i.e., 1E(a2u,eg) -1E(a1u,eg), decreases along the series Pd > Cu > Zn > H2 and also along the series OEP > P ? TFPP > TPP. The theory and date are reviewed, and it is concluded that the energy difference between the two excited triplets, i.e., 3E(a2u,eg) -3E(a1u,eg), also decreases along these series. However the condition of degeneracy, e.g., 1E(a2u,eg) - 1E(a1u,eg) = 0, occurs for different molecules in the singlet and triplet cases. Theory also suggests that if 3E(a2u,eg) > 3E(a1u,eg), the molecule should form a 2A1u cation radical and if 3E(a2u,eg) 3E(a1u,eg) the molecule should form a 2A2u radical.

Transition metal tetrapentafluorophenyl porphyrin catalyzed hydrogen evolution from acetic acid and water

The performance of Cu (1), Co (2) and Zn (3) complexes of meso-tetrakis(pentafluorophenyl)porphyrin in the electrocatalyzed evolution of hydrogen has been investigated. In acetic acid media, hydrogen evolution turnover frequency (TOF) values for complexes 1, 2 and 3 were 22.1, 19.8 and 18.1?h?1, respectively, at an overpotential of 942?mV versus Ag/AgNO3. In buffer solution at pH 7.0, the corresponding hydrogen evolution TOF values increased dramatically, to 266, 234, 218?h?1 at a similar overpotential of 878?mV versus SHE. The Faradaic yields of 1, 2, and 3 for sustained proton reduction in catalytic experiments at a glassy carbon electrode over 72?h were 89.7, 90.4 and 91.0%, respectively, with no observable catalyst decomposition.

EPR Spectra, Luminescence Data, and Radiationless Decay Processes of Copper(II) Porphyrins

For a series of copper(II) porphyrins, we report EPR data from solid solutions as well as E0 values for the first ring oxidation, emission spectra, and luminescence lifetimes in methylene chloride. Although the EPR parameters are fairly constant, the potentials vary by almost 700 mV, and the room-temperature lifetimes range from 300 ns for Cu(TC12PP) to 15 ns for Cu(TMeOPP), where TC12PP denotes 5,10,15,20-tetra(2′,6′-dichlorophenyl)porphyrin and TMeOPP denotes 5,10,15,20-tetra(4′-methoxyphenyl)porphyrin. The data show that the variation in the lifetime of the emitting π-π* state is not due to the thermal population of another excited state of either d-d or charge-transfer parentage. However, the results are consistent with a model originally introduced by Asano et al. who proposed that an important vibronic distortion occurs in the emitting trip-doublet and trip-quartet states when the excitation involves the a2u orbital of the porphyrin (Asano, M.; Kaizu, Y.; Kobayashi, H. J. Chem. Phys. 1988, 89, 6567-6576). In view of the fact that the distortion is unique to the copper systems, we suggest that it involves movement toward a sitting-atop structure, consistent with the role the d10 configuration is likely to have in the excited-state wave function.

Thermal Splitting of Bis-Cu(II) Octaphyrin(1.1.1.1.1.1.1.1) into Two Cu(II) Porphyrins

When heated, bis-Cu(II) octaphyrin(1.1.1.1.1.1.1.1) is quantitatively split into two Cu(II) porphyrins both in solution and film states, which is accompanied by large absorption spectral changes. Copyright

Metalation chemistry of meso-aryl-substituted expanded porphyrins

meso-Aryl-substituted expanded porphyrins are structural analogues of meso-aryl-substituted porphyrins. They exhibit rich and novel coordination behaviors, including multi-metal chelation due to the large cavities, spin-spin interaction arising from the proximity of metal centers, and large changes in their structural and electrochemical properties upon metalation. The recent discovery of a facile, one-pot synthesis of a series of meso-aryl-substituted expanded porphyrins enables us to investigate their metal-complexation chemistry. The aim of this Microreview is to highlight recent progress in the synthesis and characterization of metal complexes of meso-aryl-substituted expanded porphyrins. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.

The construction of C(sp3)–O bond via copper porphyrin catalyzed cross-dehydrogenative coupling reaction: Substituent and electronic effect of the catalysts

The push-pull electronic and steric effect of copper porphyrin catalysts on the cross-dehydrogenative coupling (CDC) reaction between the hydroxyl group of phenol substrates and C(sp3)-H bond have been investigated. Results showed that copper porphyrin bearing electron-withdrawing, bulky steric hindrance or heteroatom of pyridyl groups could increase the catalytic activity in the reaction. 5,10,15,20-(tetrakis(4-pyridyl)porphyrin)copper (CuTPyP) was found the best among all tested catalysts. Phenol substrates bearing various functional groups afforded moderate to excellent yields (99%). Significantly, as compared to other tested copper porphyrins, CuTPyP not only exhibited remarkable higher activity but also could shorten the reaction time from 12 to 6 h.

Observations on the Mechanochemical Insertion of Zinc(II), Copper(II), Magnesium(II), and Select Other Metal(II) Ions into Porphyrins

Building on a proof of concept study that showed the possibility of the mechanochemical insertion of some M(II) metals into meso-tetraphenylporphyrin using a ball mill as an alternative to traditional solution-based methods, we present here a detailed study of the influence of the many experimental variables on the reaction outcome performed in a planetary mill. Using primarily the mechanochemical zinc, copper, and magnesium insertion reactions, the scope and limits of the type of porphyrins (electron-rich or electron-poor meso-tetraarylporphyrins, synthetic or naturally occurring octaalkylporphyrins, and meso-triphenylcorrole) and metal ion sources suitable for this metal insertion modality were determined. We demonstrate the influence of the experimental metal insertion parameters, such as ball mill speed and reaction time, and investigated the often surprising roles of a variety of grinding agents. Also, the mechanochemical reaction conditions that remove zinc from a zinc porphyrin complex or exchange it for copper were studied. Using some standardized conditions, we also screened the feasibility of a number of other metal(II) insertion reactions (VO, Ni, Fe, Co, Ag, Cd, Pd, Pt, Pb). The underlying factors determining the rates of the insertion reactions were found to be complex and not always readily predictable. Some findings of fundamental significance for the mechanistic understanding of the mechanochemical insertion of metal ions into porphyrins are highlighted. Particularly the mechanochemical insertion of Mg(II) is a mild alternative to established solution methods. The work provides a baseline from which the practitioner may start to evaluate the mechanochemical metal insertion into porphyrins using a planetary ball mill.

Structure and dynamics processes in free-base chlorins controlled by chemical modifications of macroring and aryl groups in: Meso -positions

In this work we present the synthesis, detailed structural characterization and analysis of molecular motion for unsymmetrical pyrrolidine-fused chlorins employing NMR, UV spectroscopy and DFT theoretical calculations. In samples, the meso-rings were modified by substitution of hydrogen by fluorine in ortho1 and meta positions 2. The sample with perfluorinated ring 3 and phenyl derivative 4 were used as reference species. The assignment of signals was performed employing 2D NMR techniques. The rotational dynamics was examined by means of 1H and 19F variable-temperature (VT) 1D NMR spectroscopy and 2D EXSY experiments. The synergism of steric effect between pyrrolidine ring and meso-rings is unambiguously proved. Models 1 and 3 behave very similar, aromatic rings are rigid in temperature range 233-373 K. For sample 2 and 4 the distinct molecular dynamics was revealed. The barrier of rotation depends on localization of ring in the chlorin structure. Those which are bonded in the neighborhood of pyrrolidine ring are more rigid compared to those localized on the opposite site. The temperature is a trigger which sequentially releases the rotation of aromatic group in the desired localization. Introduction of fluorine in labeled position has influence on static geometry defined by saddling angles.