Manganese-corrole complexes in combination with a co-catalyst [PPN]X ([PPN](+)=bis(triphenylphosphoranylidene)iminium) were found to be new versatile catalysts for the polymerization of epoxides, copolymerization of epoxides with CO2, and copolymerization of epoxides with cyclic anhydrides affording a wide range of polymeric materials. This work should allow the synthesis of new types of improved innovative (co)polymers with original properties and would clearly increase the number of applications for polyesters, polycarbonates, and polyethers.
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Mechanistic insights into dioxygen activation by a manganese corrole complex: a broken-symmetry DFT study.
RSC Adv
July 2021
Department of Chemistry, Renmin University of China Beijing 100872 China
The Mn-oxygen species have been implicated as key intermediates in various Mn-mediated oxidation reactions. However, artificial oxidants were often used for the synthesis of the Mn-oxygen intermediates. Remarkably, the Mn(v)-oxo and Mn(iv)-peroxo species have been observed in the activation of O by Mn(iii) corroles in the presence of base (OH) and hydrogen donors.
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J Am Chem Soc
September 2021
Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an 710119, People's Republic of China.
Water nucleophilic attack (WNA) on high-valent terminal Mn-oxo species is proposed for O-O bond formation in natural and artificial water oxidation. Herein, we report an electrocatalytic water oxidation reaction with Mn tris(pentafluorophenyl)corrole () in propylene carbonate (PC). O was generated at the Mn potential with hydroxide, but a more anodic potential was required to evolve O with only water.
View Article and Find Full Text PDFElectrocatalytic Reduction of CO to Acetic Acid by a Molecular Manganese Corrole Complex.
Angew Chem Int Ed Engl
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Institute of Organic Chemistry, Johannes Kepler University Linz, Altenberger Straße 69, 4040, Linz, Austria.
The controlled electrochemical reduction of carbon dioxide to value added chemicals is an important strategy in terms of renewable energy technologies. Therefore, the development of efficient and stable catalysts in an aqueous environment is of great importance. In this context, we focused on synthesizing and studying a molecular Mn -corrole complex, which is modified on the three meso-positions with polyethylene glycol moieties for direct and selective production of acetic acid from CO .
View Article and Find Full Text PDFA tris-(manganese(iii))corrole-porphyrin-corrole triad: synthesis, characterization and catalytic epoxidation.
Dalton Trans
June 2019
Department of Chemistry, Indian Institute of Science Education and Research Bhopal, Bhopal Bypass Road, Bhauri, Bhopal-462066, India.
A homotrimetallic manganese(iii) corrole-porphyrin-corrole triad has been synthesized and structurally characterized. Corrole and porphyrin rings in the free base corrole-porphyrin-corrole triad are found to be roughly perpendicular to each other having a dihedral angle of 83° in the solid state. A dihedral angle of nearly 67° was found between Mn(iii)-corroles and Mn(iii)-porphyrin rings in the manganese triad complex, 1-Mn.
View Article and Find Full Text PDFElectronic Structure of Manganese Corroles Revisited: X-ray Structures, Optical and X-ray Absorption Spectroscopies, and Electrochemistry as Probes of Ligand Noninnocence.
Inorg Chem
August 2018
Department of Chemistry , UiT-The Arctic University of Norway, Tromsø N-9037 , Norway.
Presented herein is a detailed multitechnique investigation of ligand noninnocence in S = / manganese corrole derivatives at the formal Mn oxidation state. The Soret maxima of Mn[T pXPC]Cl (T pXPC = meso-tris( p-X-phenyl)corrole, where X = CF, H, Me, and OMe) were found to red-shift over a range of 37 nm with increasing electron-donating character of X. For Mn[T pXPC]Ph, in contrast, the complex Soret envelopes were found to be largely independent of X.
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