A Reactive Manganese(IV)-Hydroxide Complex: A Missing Intermediate in Hydrogen Atom Transfer by High-Valent Metal-Oxo Porphyrinoid Compounds.

ABSTRACT: High-valent metal-hydroxide species are invoked as critical intermediates in both catalytic, metal-mediated O2 activation (e.g., by Fe porphyrin in Cytochrome P450) and O2 production (e.g., by the Mn cluster in Photosystem II). However, well-characterized mononuclear MIV(OH) complexes remain a rarity. Herein we describe the synthesis of MnIV(OH)(ttppc) (3) (ttppc = tris(2,4,6-triphenylphenyl) corrole), which has been characterized by X-ray diffraction (XRD). The large steric encumbrance of the ttppc ligand allowed for isolation of 3. The complexes MnV(O)(ttppc) (4) and MnIII(H2O)(ttppc) (1·H2O) were also synthesized and structurally characterized, providing a series of Mn complexes related only by the transfer of hydrogen atoms. Both 3 and 4 abstract an H atom from the O-H bond of 2,4-di-

SUBMITTER: Zaragoza JPT 

PROVIDER: S-EPMC6066600 | biostudies-literature | 2018 Mar

REPOSITORIES: biostudies-literature