325462-39-3

Upstream product

• 6156-78-1 manganese (II) acetate tetrahydrate 
• 10028-15-6 ozone 
• 262280-87-5 manganese 5,10,15-tris(pentafluorophenyl)corrole 
• 262280-87-5 5,10,15-tris(pentafluorophenyl)corrolato-manganese(III) 
• 536-80-1 iodosylbenzene 
• 3240-34-4 [bis(acetoxy)iodo]benzene 
• 242461-32-1 1-(tert-butylsulfonyl)-2-iodosylbenzene 
• 918776-46-2 5,10,15-tris(pentafluorophenyl)corrolato(ehyl acetate)manganese(III) 
• 918776-48-4 (5,10,15-tris(pentafluorophenyl)corrole^(3-))Mn(V)=NTs 
• 7732-18-5 water 

Downstream Products

• 918776-46-2 5,10,15-tris(pentafluorophenyl)corrolato(ehyl acetate)manganese(III) 
• 262280-87-5 5,10,15-tris(pentafluorophenyl)corrolato-manganese(III) 

Relevant academic research and scientific papers

Visible light-induced formation of corrole-manganese(V)-oxo complexes: Observation of multiple oxidation pathways

Two manganese(V)-oxo corroles [MnV(Cor)O] that differ in their electronic environments were produced by visible light irradiation of highly photo-labile corrole-manganese(IV) bromates. The corrole ligands under study include 5,10,15-tris(pentafluorophenyl)corrole (TPFC), and 5,10,15-triphenylcorrole (TPC). The kinetics of oxygen transfer atom (OAT) reactions with various organic reductants by these photo-generated MnV(Cor)O were also studied in CH3CN and CH2Cl2 solutions. MnV(Cor)O exhibits remarkable solvent and ligand effect on its reactivity and spectral behavior. In the more electron-deficient TPFC system and in the polar solvent CH3CN, MnV(Cor)O returned MnIII corrole in the end of oxidation reactions. However, in the less polar solvent CH2Cl2 or in the less electron-deficient TPC system, MnIV product was formed instead of MnIII. Furthermore, with the same substrates and in the same solvent, the order of reactivity of MnV(Cor)O was TPC>?TPFC, which is inverted from that expected based on the electron-demand of corrole ligands. Our spectral and kinetic results in this study provide compelling evidence in favor of multiple oxidation pathways, where MnV(Cor)O may serve as direct two-electron oxidant or undergo a disproportionation reaction to form a manganese(VI)-oxo corrole as the true oxidant. The choice of pathways is strongly dependent on the nature of the solvent and the corrole ligand.

Dioxygen Activation and O-O Bond Formation Reactions by Manganese Corroles

Activation of dioxygen (O2) in enzymatic and biomimetic reactions has been intensively investigated over the past several decades. More recently, O-O bond formation, which is the reverse of the O2-activation reaction, has been the focus of current research. Herein, we report the O2-activation and O-O bond formation reactions by manganese corrole complexes. In the O2-activation reaction, Mn(V)-oxo and Mn(IV)-peroxo intermediates were formed when Mn(III) corroles were exposed to O2 in the presence of base (e.g., OH-) and hydrogen atom (H atom) donor (e.g., THF or cyclic olefins); the O2-activation reaction did not occur in the absence of base and H atom donor. Moreover, formation of the Mn(V)-oxo and Mn(IV)-peroxo species was dependent on the amounts of base present in the reaction solution. The role of the base was proposed to lower the oxidation potential of the Mn(III) corroles, thereby facilitating the binding of O2 and forming a Mn(IV)-superoxo species. The putative Mn(IV)-superoxo species was then converted to the corresponding Mn(IV)-hydroperoxo species by abstracting a H atom from H atom donor, followed by the O-O bond cleavage of the putative Mn(IV)-hydroperoxo species to form a Mn(V)-oxo species. We have also shown that addition of hydroxide ion to the Mn(V)-oxo species afforded the Mn(IV)-peroxo species via O-O bond formation and the resulting Mn(IV)-peroxo species reverted to the Mn(V)-oxo species upon addition of proton, indicating that the O-O bond formation and cleavage reactions between the Mn(V)-oxo and Mn(IV)-peroxo complexes are reversible. The present study reports the first example of using the same manganese complex in both O2-activation and O-O bond formation reactions.

Synthetic and mechanistic investigations on manganese corrole-catalyzed oxidation of sulfides with iodobenzene diacetate

Manganese corrole complexes catalyze the efficient oxidation of organic sulfides to sulfoxides with iodobenzene diacetate [PhI(OAc)2] as a mild oxygen source in the presence of small amounts of water. Various substituted thioanisoles can be eff

Visible-light photolysis of corrole-manganese(IV) nitrites to generate corrole-manganese(V)-oxo complexes

Photolysis of highly photo-labile corrole-manganese(IV) nitrites by visible light was studied in three corrole systems with different electronic environments. As observed in all three systems, homolytic cleavage of O–N bond of nitrite ligand resulted in one-electron photo-oxidation to generate manganese(V)-oxo corroles, as determined by their distinct UV–vis spectra and kinetic behaviors. The spectral and kinetic results are rationalized by a multiple oxidation model, where the electron-demand MnV-oxo species may serve as direct two-electron oxidant for oxygen atom transfer reactions and less electron-demand systems undergo a disproportionation reaction to form a putative manganese(VI)-oxo corrole as the true oxidant.

Oxygen atom transfer reactions from sterically encumbered brominated (oxo)manganese(V) corroles to styrene

Seven A3-And trans-A2B manganese(III) corroles (1-7-Mn) differing widely in their electronic and steric features were synthesized and transformed to their corresponding β-brominated manganese(III) corroles derivatives (1a-7a-Mn). Their corresponding (oxo)

Valence Tautomerization of High-Valent Manganese(V)-Oxo Corrole Induced by Protonation of the Oxo Ligand

The addition of an organic acid to the manganese(V)-oxo corrole complex (tpfc)MnV(O) (tpfc = 5,10,15-tris(pentafluorophenyl)corrole) induces valence tautomerization resulting in the formation of (tpfc+?)MnIV(OH) in acetoni

Solvent effects on the catalytic activity of manganese(III) corroles

Four Mn(III) corroles that differ in their electronic environments based on meso-substitution by pentafluorophenyl and phenyl groups were synthesized and characterized by spectroscopic techniques. Utilization of these Mn(III) corroles for styrene oxidation using iodosylbenzene (PhIO) as oxygen source in toluene, dichloromethane (DCM), DMF, DMAc, THF and DMSO revealed a remarkable effect of solvent on the catalytic activity. Furthermore, the transformation of Mn(III) corroles into their corresponding Mn(V)-oxo corroles, and subsequent treatment with styrene also indicated that more electron-deficient Mn(V)-oxo corroles exhibit higher reactivity in toluene and DCM, while less electron-deficient Mn(V)-oxo corroles exhibit higher reactivity in DMF and DMAc. A significant difference in the observed rates of reaction suggest that the catalytic oxidation of styrene by manganese corroles may proceed through different pathways, and is strongly solvent-dependent.

Solvent effects on oxygen atom transfer reaction between manganese(V)-oxo corrole and alkene

Pseudo-first order reaction rate constants of 5,10,15- tris(pentafluorophenyl)corrole Mn(V)-oxo (F15CMn(V)-oxo), 5,15-bis(pentafluorophenyl)-10-(phenyl)corrole Mn(V)-oxo (F10CMn(V)- oxo), 5,15-bis(phenyl)-10-(pentafluorophenyl)corrole Mn(V)-oxo (F 5CMn(V)-oxo) and 5,10,15-tris(phenyl)corrole Mn(V)-oxo (F 0CMn(V)-oxo) with a series of alkene substrates in different solvents were determined by UV-vis spectroscopy. The results indicated that the oxygen atom transfer pathway between Mn(V)-oxo corrole and alkene is solvent-dependent.

Manganese(v)-oxo corroles in hydride-transfer reactions

Hydride transfer from dihydronicotinamide adenine dinucleotide (NADH) analogues to manganese(v)-oxo corroles proceeds via proton-coupled electron transfer, followed by rapid electron transfer. The redox potentials (E red) of manganese(v)-oxo corroles exhibit a good correlation with their reactivity in hydride-transfer reactions.

Oxygen atom transfer reactions from isolated (Oxo)manganese(V) corroles to sulfides

A series of five free-base corroles were metalated and brominated to form 10 manganese(III) corroles. Two of the free-base corroles and six manganese(III) corroles were analyzed by X-ray crystallography, including one complex that may be considered a tran