First Synthesis of Perfluorinated Corrole and Its MnO Complex

Abstract

A novel perfluorinated corrole, 2,3,7,8,12,13,17,18-octafluoro-5,10,15-tris(pentafluorophenyl)corrole, and its manganese(III) and oxomanganese(V) derivatives have been synthesized. The perfluorinated manganese corrolate exhibited excellent reactivity and stability in the catalytic oxidation of alkenes with iodosylbenzene.

Laser Flash Photolysis Generation and Kinetic Studies of Corrole–Manganese(v)‐Oxo Intermediates

“…[6] Perhalogenation of the corrole macrocycle with bromine or fluorine results in increased reactivity as judged by turnover numbers and bulk oxidation velocities for the corrole-manganese complexes under catalytic conditions with PhIO as the sacrificial oxidant. [7,8] No kinetic information has been reported for corrole-manganese-oxo reactions, however, and the mechanisms are not well understood. For example, oxidation of the (TPFC)Mn III complex with ozone gives the (TPFC)Mn V (O) species, which does not react with styrene at room temperature, [5] an observation that led Gross and co-workers to the conclusion that the active oxidant in the catalytic process has the metal ion in a higher oxidation state than manganese(v).…”

Study of Structure−Properties Relationship for Lanthanide Tetrapyrrolic Macrocycles Modified with Aminopolycarboxylate Substituents

“…[2] Until that time corroles had obtained by complexed multi-step pathway, with a total yield of compounds (even the most simple structure) less than 0.1 %. [3] Both porphyrins and corroles already prove itself as efficient catalysts for oxidation [4] and reduction reactions, [5] as a basis for carbon monoxide sensors, [6] as optodes for determination the pH, [7] as ion-selective electrodes, [8] as dyesensitized solar cells [9] and also in medicine as fluorescent markers. [10] Application of corroles in most cases is based on their fluorescent properties.…”

A Perspective of One‐Pot Pyrrole–Aldehyde Condensations as Versatile Self‐Assembly Processes

“…Chang and co-workers also failed to isolate (F 8 TPFC)H 3 by using the original conditions of the one-pot corrole synthesis. [93] However, they did isolate what appeared to be a linear bilene intermediate that had apparently failed to cyclize, presumably because of the low nucleophilicity of the 3,4-difluoropyrrole units. Irradiation of this species in CH 2 Cl 2 under an ammonia atmosphere then led to the formation of (F 8 TPFC)H 3 (Scheme 14).…”

“…[91,92] Shown against the green background is perfluorinated triphenylcorrole ((F 8 TPFC)H 3 ), recently prepared by Chang and co-workers. [93] Angewandte Chemie A. Ghosh relatively long period of heating in the solvent-free procedure also led to the formation of (F 8 TPFC)H 3 in a low but acceptable yield of 5 %. [93] We believe that these findings greatly expand the scope of the solvent-free corrole synthesis, because not only does the reaction occur with a variety of aldehydes, but it appears that it may be possible to use a variety of 3,4-substituted pyrroles as well.…”

“…[93] Angewandte Chemie A. Ghosh relatively long period of heating in the solvent-free procedure also led to the formation of (F 8 TPFC)H 3 in a low but acceptable yield of 5 %. [93] We believe that these findings greatly expand the scope of the solvent-free corrole synthesis, because not only does the reaction occur with a variety of aldehydes, but it appears that it may be possible to use a variety of 3,4-substituted pyrroles as well. Thus, like the onepot porphyrin synthesis, the one-pot corrole synthesis has emerged as a member of an exclusive group of self-assemblybased synthetic reactions that lend themselves to a substantial degree of systematic variation and optimization.…”