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Issue 14, 2011
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High-valent iron and manganese complexes of corrole and porphyrin in atom transfer and dioxygen evolving catalysis

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Abstract

Manganese(V) imido complexes of 5,10,15-tris(pentafluorophenyl)corrole (H3tpfc) can be prepared by the reaction of MnIII(tpfc) and organic nitrene generated from either photolytic or thermal activation of organic azides. The terminal imido complexes of manganese(V) were among the first structurally characterized examples of MnV terminal imido complexes in the literature. They feature a short Mn[triple bond, length as m-dash]N triple bond and a nearly linear M[triple bond, length as m-dash]N–C angle. The ground state of (tpfc)MnV(NAr) is singlet. Contrary to expectations, arylimido complexes of manganese(V) were stable to moisture and did not undergo [NR] group transfer to olefins. Manganese(V) imido corrole with an activated tosyl imido ligand was prepared from iodoimine (ArINTs) and manganese(III) corrole. The resulting complex (tpfc)Mn(NTs) is paramagnetic (S = 1), hydrolyzes to (tpfc)Mn(O) in the presence of water, abstracts hydrogen atoms from benzylic C–H bonds, and catalyzes aziridination of alkenes. Mechanistic studies on the aziridination and hydrogen atom transfer reactions are reviewed. This perspective also describes the reaction chemistry of the heme enzyme chlorite dismutase, the mechanism by which dioxygen is formed on a single-metal site, and recent advances in functional modelling of this enzyme. We also compare the reactivity of water-soluble ironversusmanganese porphyrins towards the chlorite anion.

Graphical abstract: High-valent iron and manganese complexes of corrole and porphyrin in atom transfer and dioxygen evolving catalysis

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Publication details

The article was received on 05 Oct 2010, accepted on 30 Nov 2010 and first published on 31 Jan 2011


Article type: Perspective
DOI: 10.1039/C0DT01341B
Citation: Dalton Trans., 2011,40, 3435-3444
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    High-valent iron and manganese complexes of corrole and porphyrin in atom transfer and dioxygen evolving catalysis

    M. M. Abu-Omar, Dalton Trans., 2011, 40, 3435
    DOI: 10.1039/C0DT01341B

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