67161-73-3

Upstream product

• 34557-72-7 (5,10,15,20-tetraphenylporphyrinato)manganese(III) chloride 
• 58356-65-3 manganese(III) meso-tetraphenylporphyrin acetate 

Downstream Products

• 97073-98-8 bis(2,6-lutidine-N-oxide)(tetraphenylporphinato)manganese(III) perchlorate - heptane(1/1) 
• 32195-55-4 5,10,15,20-tetraphenyl-21 H,23-H-porphine manganese(III)chloride 
• 32195-55-4 manganese (III) meso-tetraphenylporphyrin chloride 
• 97170-98-4 bis(N,N-dimethylformamide)(tetraphenylporphinato)manganese(III) perchlorate 

Relevant academic research and scientific papers

Laser flash photolysis generation and kinetic studies of porphyrin-manganese-oxo intermediates. Rate constants for oxidations effected by porphyrin-MnV-oxo species and apparent disproportionation equilibrium constants for porphyrin-MnIV-oxo species

Porphyrin-manganese(V)-oxo and porphyrin-manganese(IV)-oxo species were produced in organic solvents by laser flash photolysis (LFP) of the corresponding porphyrin-manganese(III) perchlorate and chlorate complexes, respectively, permitting direct kinetic studies. The porphyrin systems studied were 5,10,15,20-tetraphenylporphyrin (TPP), 5,10,15,20- tetrakis(pentafluorophenyl)porphyrin (TPFPP), and 5,10,15,20-tetrakis(4- methylpyridinium)porphyrin (TMPyP). The order of reactivity for (porphyrin)MnV(O) derivatives in self-decay reactions in acetonitrile and in oxidations of substrates was (TPFPP) > (TMPyP) > (TPP). Representative rate constants for reaction of (TPFPP)MnV(O) in acetonitrile are k = 6.1 ×105 M-1 s-1 for cis-stilbene and k = 1.4 × 105 M-1 s-1 for diphenylmethane, and the kinetic isotope effect in oxidation of ethylbenzene and ethylbenzene-d10 is kH/kD = 2.3. Competitive oxidation reactions conducted under catalytic conditions display approximately the same relative rate constants as were found in the LFP studies of (porphyrin)MnV(O) derivatives. The apparent rate constants for reactions of (porphyrin)MnIV(O) species show inverted reactivity order with (TPFPP) IV(O) disproportionates to (porphyrin)MnIIIX and (porphyrin)MnV(O), which is the primary oxidant, and the equilibrium constants for disproportionation of (porphyrin)MnIV(O) are in the order (TPFPP) V(O) with (TPFPP)MnIIICl to give (TPFPP)MnIV-(O) (k = 5 × 108 M-1 s -1) and disproportionation reaction of (TPP)MnIV(O) to give (TPP)MnV(O) and (TPP)-MnIIIX (k ≈ 2.5 × 109 M-1 s-1) were observed. The relative populations of (porphyrin)MnV(O) and (porphyrin)MnIV(O) were determined from the ratios of observed rate constants for self-decay reactions in acetonitrile and oxidation reactions of cis-stilbene by the two oxo derivatives, and apparent disproportionation equilibrium constants for the three systems in acetonitrile were estimated. A model for oxidations under catalytic conditions is presented.

The use of perchlorato(tetraphenylporphinato)manganese(III) as a reagent for the spectrophotometric determination of anions in nonaqueous solvents

Perchlorato(tetraphenylporphinato)manganese(III) (TPPMnClO4) is shown to be a useful reagent for the determination of a variety of anions in nonaqueous media.The analysis is based on the displacement of coordinated perchlorate by more strongly coordinating anions as monitored spectrophotometrically.The procedure is demonstrated for the determination of tetra-alkylammonium salts of nitrate, nitrite, chloride, bromide, iodide, acetate, trifluoroacetate, cyanate, and thiocyanate in acetonitrile.Relative precisions and accuracies of the order of five parts per thousand are indicated.Key words: perchlorato(tetraphenylporphinato)manganese(III), spectrophotometric determination of anions, anions in nonaqueous media.

Efficient reduction of dioxygen with ferrocene derivatives, catalyzed by metalloporphyrins in the presence of perchloric acid

Reduction of dioxygen with ferrocene derivatives (Fc) is catalyzed by metalloporphyrins (MTPP+: M = Co, Fe, Mn; TPP = tetraphenylporphyrin) or Co(TIM)3+ (TIM: a tetraaza macrocyclic ligand) in the presence of HClO4 in acetonitrile (MeCN). Electron transfer from Fc to MTPP+ is the rate-determining step for the MTPP+-catalyzed oxidation of Fc by dioxygen, when the rate is independent of the concentration of dioxygen or HClO4. On the other hand, the rate of electron transfer from Fc to Co(TIM)3+ is accelerated by the presence of HClO4 and dioxygen. The rates of these electron-transfer reactions are discussed in light of the Marcus theory of electron transfer to distinguish between outer-sphere and inner-sphere electron-transfer processes. The strong inner-sphere nature of metalloporphyrins in the electron-transfer reactions with dioxygen in the presence of HClO4 plays an essential role in the catalytic reduction of dioxygen.

Structural and electronic properties of six-coordinate manganese(III) porphyrin cations. Crystal and molecular structure of bis(N,N-dimethylformamide)(tetraphenylporphinato)manganese(III) perchlorate, [MnIIITPP(DMF)2]+ClO4-

In toluene or chloride-free chloroform solutions of Mn-TPP(ClO4) in the presence of the neutral ligands L = dimethylformamide, dimethylacetamide, 1-methylimidazole, dimethyl sulfoxide, and tetrahydrofuran the six-coordinate cationic complexes [MnIIITPP(L)2]+ClO4- form. One of these complexes, bis(N,N-dimethylformamide)(tetraphenylporphinato)manganese(m) perchlorate [MnIIITPP(DMF)2]+ClO4- (1), was isolated, purified, and characterized in detail. The electronic spectra, H NMR spectra and magnetic properties of 1 in solution establish that this complex contains a high-spin S = 2 MnIII atom with a (dxzπ,dyzπ)2(dxy) 1(d z2σ)1 electronic configuration. The variable-temperature 1H NMR data furthermore rule out any change in ground electronic state over the temperature range -30 to +55 °C. All the cationic MnIII porphyrin complexes undergo fast exchange of the neutral axial ligands, L, on the NMR time scale even at -40 °C. Complex 1 forms solvate-free crystals in space group C2/c. The unit cell has a = 17.7386 (43) A?, b = 17.7182 (60) A?, c = 15.9477 (56) A?, β = 118.693 (22)° and Z = 4. The structure was solved by the heavy-atom method and converged with a final R = 0.0841. The six-coordinate S = 2 MnIII atom displays the predicted tetragonal elongation with very long MnIII-O(DMF) bonds (2.217 (4) A?). Complex 1 shows a temperature-dependent alteration of coordination geometry in solution with the six-coordinate species predominating below -10 °C and a five-coordinate species predominating above +10 °C.