Cyclooctapyrroles such as 1–3 tend to form during the condensation of dipyrrolic units if cyclization to cyclotetrapyrroles is hindered for conformational reasons. These macrocycles are chiral and might afford interesting complexes with metal ions. Their most intriguing feature is their unusual figure‐eight conformation.
The synthesis, spectroscopic characterization and electrochemistry of four Mn(III) and Mn(IV) octaethylcorroles are reported and the potentials of the Mn(III) / Mn(IV) and Mn(IV) / Mn(III) processes examined as a function of the axial ligand. The investigated compounds are represented as ( OEC ) Mn , ( OEC ) MnCl , ( OEC ) Mn ( py ) and ( OEC ) Mn ( C 6 H 5) where OEC is the trianion of octaethylcorrole. The first one-electron oxidation of ( OEC ) Mn III and ( OEC ) Mn III ( py ) in PhCN or pyridine containing 0.1 M TBAP leads to the facile formation of a Mn(IV) species while the first one-electron reduction of ( OEC ) Mn IV Cl and ( OEC ) Mn IV ( C 6 H 5) in the same two solvents leads to the Mn(III) corrole. All other redox reactions occur at the corrole macrocycle to give π-cation radicals or π-anion radicals and there is no evidence for electrogeneration of a compound with a Mn(II) oxidation state as is the case for manganese(III) porphyrins which are all easily reduced to the Mn(II) state in nonaqueous media. The products of each Mn(III)/Mn(IV) redox reaction were characterized by UV-visible and/or ESR spectroscopy and the structures of ( OEC ) MnCl , ( OEC ) Mn ( py ) and ( OEC ) Mn ( C 6 H 5) were determined by single-crystal X-ray diffraction.
Die Cyclooctapyrrole 1‐3 sind eindrucksvolle Beispiele dafür, daß bei der Kondensation von dipyrrolischen Bausteinen die Bildung von Cyclooctapyrrolen gegenüber der entsprechender Cyclotetrapyrrole bevorzugt sein kann, wenn die Cyclisierung zu letzteren konformativ behindert ist. Die Makrocyclen sind chiral und könnten mit Metall‐Ionen interressante Komplexe bilden. Am faszinierendsten ist sicherlich ihre ungewöhnliche Konformation, die an das Aussehen der Zahl 8 erinnert.
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