129707-76-2

Upstream product

• 25440-14-6 tetrakis(pentafluorophenyl)porphyrin 
• 68-12-2 N,N-dimethyl-formamide 
• 506-59-2 N,N-dimethylammonium chloride 

Downstream Products

• 156191-12-7 chloro[5,10,15,20-tetrakis(4-dimethylamino-2,3,5,6-tetrafluorophenyl)porphyrinate]iron(III) 

Relevant academic research and scientific papers

Metalloporphyrins for quadratic nonlinear optics

CuII- and ZnII-based donor-acceptor porphyrins have been examined for second-order nonlinear optics using the hyper-Rayleigh scattering technique at 1064 nm. Introduction of the metal ions enhances the first hyperpolarizability (β) of the free-base donor-acceptor porphyrins significantly. The open shell CuII (d9) has a greater influence on β of these porphyrin systems than the closed shell ZnII (d10). The high β values in the ZnII porphyrins are understood in terms of the change in dipole moments upon excitation within the context of the two-state model as well as two-photon resonance enhancement. In CuII porphyrin complexes a large number of excited states seem to contribute to β with, perhaps, a little contribution from two-photon resonance at the excitation wavelength.

Hydrogen-atom abstraction reactions by manganese(V)- and manganese(IV)-oxo porphyrin complexes in aqueous solution

High-valent manganese(IV or V)-oxo porphyrins are considered as reactive intermediates in the oxidation of organic substrates by manganese porphyrin catalysts. We have generated MnV- and MnIV-oxo porphyrins in basic aqueous solution and investigated their reactivities in C-H bond activation of hydrocarbons. We now report that MnV- and Mn IV-oxo porphyrins are capable of activating C-H bonds of alkylaromatics, with the reactivity order of MnV-oxo>Mn IV-oxo; the reactivity of a MnV-oxo complex is 150 times greater than that of a MnIV-oxo complex in the oxidation of xanthene. The C-H bond activation of alkylaromatics by the MnV- and Mn IV-oxo porphyrins is proposed to occur through a hydrogen-atom abstraction, based on the observations of a good linear correlation between the reaction rates and the C-H bond dissociation energy (BDE) of substrates and high kinetic isotope effect (KIE) values in the oxidation of xanthene and dihydroanthracene (DHA). We have demonstrated that the disproportionation of MnIV-oxo porphyrins to MnV-oxo and MnIII porphyrins is not a feasible pathway in basic aqueous solution and that Mn IV-oxo porphyrins are able to abstract hydrogen atoms from alkylaromatics. The C-H bond activation of alkylaromatics by MnV- and MnIV-oxo species proceeds through a one-electron process, in which a MnIV-oxo porphyrin is formed as a product in the C-H bond activation by a MnV-oxo porphyrin, followed by a further reaction of the MnIV-oxo porphyrin with substrates that results in the formation of a MnIII porphyrin complex. This result is in contrast to the oxidation of sulfides by the MnV-oxo porphyrin, in which the oxidation of thioanisole by the MnV-oxo complex produces the starting Mn III porphyrin and thioanisole oxide. This result indicates that the oxidation of sulfides by the MnV-oxo species occurs by means of a two-electron oxidation process. In contrast, a MnIV-oxo porphyrin complex is not capable of oxidizing sulfides due to a low oxidizing power in basic aqueous solution.

The oxidation of ethylbenzene and other alkylaromatics by dioxygen catalysed by iron(III) tetrakis(pentafluorophenyl)porphyrin and related iron porphyrins

The oxidation of ethylbenzene with dioxygen catalysed by iron(III) porphyrins in a solvent free system has been studied over the temperature range 30-110°C. The time dependence of the formation of the three main products, 1-phenylethanol, acetophenone and 1-phenylethyl hydroperoxide, and the fate of the iron porphyrin are interpreted in terms of a free radical autoxidation mechanism. The yields of the oxidation products are determined by the rate of reaction and by the lifetime of the catalyst. Catalyst degradation is shown to involve reaction of the porphyrin ligand with 1-phenylethoxyl and 1-phenylethylperoxyl radicals. The disadvantages of increased induction periods and longer reaction times of the oxidations observed at lower reaction temperatures are counter balanced by increased catalyst turnovers. Less extensive studies on the oxidations of toluene, cumene, (2-methylpropyl)-benzene and tert-butylbenzene support the overall mechanism proposed for ethylbenzene. A comparative study using the catalysts iron(III) 2,3,7,8,12,13,17,18-octachloro-5,10,15,20-tetrakis-(2,6-dichlorophenyl)porphyrin and iron(III) tetrakis(pentafluorophenyl)porphyrin and five of its derivatives reveals that halogenation of the β-pyrrole positions markedly increases the activity of the catalysts but not the stability of the porphyrin towards degradation. The highest yields were obtained with the μ-oxodimer of iron(III) tetrakis(pentafluorophenyl)porphyrin and iron(III) tetrakis(4-dimethylamino-2,3,5,6-tetrafluorophenyl)-porphyrin.

Syntheses and spectroscopic characterization of (T(P-Me2N)F4PP)H2 and (7(p-Me2N)F4PP)M where 7(p-Me2N)F4PP is the dianion of meso-tetrakis(o,o,w,w-tetrafluoro-p-(dimethylamino)phenyl)-porphyrin and M = Co(II), Cu(II), or Ni(II)

The reaction of cobalt acetate with (TF5PP)H2 (where TF5PP = the dianion of meso-tetrakis(pentafluoro-phenyl)porphyrin) leads to the formation of different metalloporphyrin products depending on solvent. In acetonitrile, (TF5PP)Co is the expected and obtained product of metalation. In contrast, the reaction between (TF5PP)H2 and cobalt acetate in dimethylformamide leads to (T(p-Me2N)F4PP)Co where T(p-Me2N)F4PP = the dianion of meso-tetrakis(o,o,w,m-tetra-fluoro-p-(dimethylamino)phenyl)porphyrin. The formation of a dimethylamino-substituted complex in DMF is not unique to cobalt derivatives, and (T(P-Me2N)F4PP)H2, (T(P-Me2N)F4PP)Cu, or (T(P-Me2N)F4PP)Ni were synthesized from (TF5PP)H2 in almost 100% yield. Each T(p-Me2N)F4PP complex was isolated and characterized by 1H NMR, 19F NMR, and UV-visible spectroscopy as well as by mass spectrometry. These compounds provide the first examples for substituted tetraphenylporphyrins where the four phenyl rings contain both electron-withdrawing and electron-donating substituents. The pentafluoro-substituted Co(II) derivative, (TF5PP)Co, was also synthesized and spectroscopically characterized. In addition, both Co(II) porphyrins were analyzed by X-ray single-crystal diffraction. (TF5PP)Co crystallizes in the monoclinic space group I2/c, with a = 29.200 (13) ?, b = 6.552 (2) ?, c = 26.381 (10) ?, β = 104.13 (3)°, and Z = 4 while (T(p-Me2N)F4PP)Co is found to crystallize in the triclinic space group P1? with a = 13.638 (9) ?, b = 14.645 (8) ?, c = 16.677 (9) ?, α = 79.98 (4)°, β= 77.89 (5)°, γ = 65.92 (4)°, and Z = 2.