262280-87-5Relevant academic research and scientific papers
Valence Tautomerization of High-Valent Manganese(V)-Oxo Corrole Induced by Protonation of the Oxo Ligand
Bougher, Curt J.,Liu, Shuo,Hicks, Scott D.,Abu-Omar, Mahdi M.
, p. 14481 - 14487 (2015)
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
Catalytic two-electron reduction of dioxygen by ferrocene derivatives with manganese(V) corroles
Jung, Jieun,Liu, Shuo,Ohkubo, Kei,Abu-Omar, Mahdi M.,Fukuzumi, Shunichi
, p. 4285 - 4291 (2015)
Electron transfer from octamethylferrocene (Me8Fc) to the manganese(V) imidocorrole complex (tpfc)MnV(NAr) [tpfc = 5,10,15-tris(pentafluorophenyl)corrole; Ar = 2,6-Cl2C6H3] proceeds efficiently to give an octamethylferrocenium ion (Me8Fc+) and [(tpfc)MnIV(NAr)]- in acetonitrile (MeCN) at 298 K. Upon the addition of trifluoroacetic acid (TFA), further reduction of [(tpfc)MnIV(NAr)]- by Me8Fc gives (tpfc)MnIII and ArNH2 in deaerated MeCN. TFA also results in hydrolysis of (tpfc)MnV(NAr) with residual water to produce a protonated manganese(V) oxocorrole complex ([(tpfc)MnV(OH)]+) in deaerated MeCN. [(tpfc)MnV(OH)]+ is rapidly reduced by 2 equiv of Me8Fc in the presence of TFA to give (tpfc)MnIII in deaerated MeCN. In the presence of dioxygen (O2), (tpfc)MnIII catalyzes the two-electron reduction of O2 by Me8Fc with TFA in MeCN to produce H2O2 and Me8Fc+. The rate of formation of Me8Fc+ in the catalytic reduction of O2 follows zeroth-order kinetics with respect to the concentrations of Me8Fc and TFA, whereas the rate increases linearly with increasing concentrations of (tpfc)MnV(NAr) and O2. These kinetic dependencies are consistent with the rate-determining step being electron transfer from (tpfc)MnIII to O2, followed by further proton-coupled electron transfer from Me8Fc to produce H2O2 and [(tpfc)MnIV]+. Rapid electron transfer from Me8Fc to [(tpfc)MnIV]+ regenerates (tpfc)MnIII, completing the catalytic cycle. Thus, catalytic two-electron reduction of O2 by Me8Fc with (tpfc)MnV(NAr) as a catalyst precursor proceeds via a MnIII/MnIV redox cycle.
Visible-light photolysis of corrole-manganese(IV) nitrites to generate corrole-manganese(V)-oxo complexes
Lee, Ngo Fung,Malone, Jonathan,Jeddi, Haleh,Kwong, Ka Wai,Zhang, Rui
, p. 27 - 30 (2017)
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.
CO2 Fixation with Epoxides under Mild Conditions with a Cooperative Metal Corrole/Quaternary Ammonium Salt Catalyst System
Tiffner, Maximilian,Gonglach, Sabrina,Haas, Michael,Sch?fberger, Wolfgang,Waser, Mario
supporting information, p. 1048 - 1051 (2017/05/26)
The cooperative catalytic activity of several metal corrole complexes in combination with tetrabutyl-ammonium bromide (TBAB) has been investigated for the reaction of epoxides with CO2 leading to cyclic carbonates. It was found that the use of just 0.05 mol % of a manganese(III)corrole with 2 mol % TBAB exhibits excellent catalytic activity under an atmosphere of CO2.
Oxygen atom transfer reactions from sterically encumbered brominated (oxo)manganese(V) corroles to styrene
Mahmood, Mian Hr,Wang, Hua-Hua,Liu, Hai-Yang,Chang, Chi-Kwong
, p. 1238 - 1250 (2016/02/18)
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)
Solvent effects on the catalytic activity of manganese(III) corroles
Wang, Qi,Zhang, Yang,Yu, Lan,Yang, Hong,Mahmood, Mian HR,Liu, Hai-Yang
, p. 316 - 325 (2014/06/09)
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.
Electron deficient manganese(III) corrole catalyzed oxidation of alkanes and alkylbenzenes at room temperature
Bose, Suranjana,Pariyar, Anand,Biswas, Achintesh Narayan,Das, Purak,Bandyopadhyay, Pinaki
experimental part, p. 1193 - 1197 (2012/01/13)
At room temperature electron deficient manganese (III) corrole complexes (1-3) were successfully employed as catalysts in the oxidation of alkanes and alkylbenzenes using m-chloroperbenzoic acid (m-CPBA) as the terminal oxidant. Adamantane has been selectively hydroxylated to adamantane 1-ol and 2-ol with higher preference for the tertiary position. Cyclohexane has also been oxidized. The present oxidizing system also oxidizes toluene, ethylbenzene and diphenylmethane. High valent oxomanganese(V) species has been proposed to be the active oxidant. The high-valent oxomanganese(V) corrole undergoes hydrogen atom transfer (HAT) reaction with 2,4,6-tri-t-butylphenol (TTBP) resulting in the formation of oxidized phenoxyl radicals. Kinetic studies have led to the determination of second-order rate constants for the hydrogen atom transfer reactions. The kinetic experiments reveal a first order reaction rate dependence on the concentration of catalyst as well as on that of the oxidant.
Manganese(III) corrole catalyzed selective oxidation of alcohols to carbonyl compounds by tert-butyl hydroperoxide under mild condition
Bose, Suranjana,Pariyar, Anand,Biswas, Achintesh Narayan,Das, Purak,Bandyopadhyay, Pinaki
experimental part, p. 446 - 449 (2011/12/15)
Mild oxidation of alcohols has been achieved with tert-butylhydroperoxide catalyzed by electron deficient manganese(III) corroles at room temperature. The catalysts used in this study showed high activity in the oxidation of benzylic alcohols to the corre
Manganese(v)-oxo corroles in hydride-transfer reactions
Han, Yejee,Lee, Yong-Min,Mariappan, Mariappan,Fukuzumi, Shunichi,Nam, Wonwoo
, p. 8160 - 8162 (2010/12/19)
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
Kumar, Anil,Goldberg, Israel,Botoshansky, Mark,Buchman, Yekaterina,Gross, Zeev
experimental part, p. 15233 - 15245 (2011/01/08)
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
