67161-73-3

Basic information

• Product Name: 5,10,15,20-tetraphenylporphyrin-manganese(III) perchlorate
• Synonyms: 5,10,15,20-tetraphenylporphyrin-manganese(III) perchlorate
• CAS NO: 67161-73-3
• Molecular Weight: 767.122
• Mol File: 67161-73-3.mol
• Article Data: 4

Chemical Properties

• CAS DataBase Reference: 5,10,15,20-tetraphenylporphyrin-manganese(III) perchlorate(CAS DataBase Reference)
• NIST Chemistry Reference: 5,10,15,20-tetraphenylporphyrin-manganese(III) perchlorate(67161-73-3)
• EPA Substance Registry System: 5,10,15,20-tetraphenylporphyrin-manganese(III) perchlorate(67161-73-3)

Safety Data

• Hazardous Substances Data: 67161-73-3(Hazardous Substances Data)

Upstream product

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

Downstream Products

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

Relevant articles and documents

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.

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.