Abstract

AbstractThis work shows the synthesis and structural, spectroscopic, and electrochemical properties of MnIII complexes supported with pyrrole‐ and indolecarboxamide ligands. In all cases, the respective ligand constitutes a N4 coordination sphere about the MnIII ion. The MnIII complexes of pyrrolecarboxamide ligands are square pyramidal with a fifth Cl atom, whereas analogous complexes of indolecarboxamide ligands are essentially square planar. Electrochemical studies reveal highly negative MnIII/II and moderately positive MnIV/III redox potentials. In situ generated Mn4+ species of the pyrrolecarboxamide ligands were characterized by absorption and electron paramagnetic resonance spectroscopy. All complexes functioned as catalysts in olefin epoxidation reactions by using PhIO as the oxo‐transfer agent. All complexes also acted as Lewis acid catalysts for ring‐opening reactions of assorted epoxides with various nucleophiles. We also show a one‐pot, two‐step epoxidation reaction followed by ring opening, which illustrates the catalytic significance of the present complexes. Importantly, MnIII complexes carrying electron‐donating substituents on the ligand were found to be better catalysts.

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