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Synthesis and redox...
Abstract
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- The Mn complexated corrole [T(4-NO2P)Corr]Mn(py) (3) has been prepared (py = pyridine) where [T(4-NO2P)Corr] is the trianion of the electron-poor 5,10,15-tris(4-nitrophenyl)-corrole (1). The preparation of 3 includes a new synthetic method to form the corrole ligand 1 in a two-step synthesis. The Mn(III) complex gives a parallel mode EPR signal centered around g = 8.2 with six distinct hyperfine lines (A(parallel to) = 139 x 10(-4) cm(-1)). Electrochemically 3 undergoes one reversible oxidation (E-1/2 = 0.12 V vs Fc) and two reversible reductions (E-1/2 = -1.45, -1.61 V). The oxidation is metal-centered and the product has been characterized by EPR spectroscopy as an S = 3/2 Mn(IV) species with no indication for oxidation of the macrocycle. The reductions of complex 3 are ligand based, and at the potential of the second reduction step a stable nitrogen centered radical with g = 2.0055 is generated. Chemical oxidation of 3 by iodosobenzene yields a Mn(IV) complex and epoxidation of cis-stilbene is not catalyzed by the Mn complex.
Keyword
- manganese
- corrole
- valence tautomerization
- electrochemistry
- EPR spectroscopy
- transition-metal centers
- high-spin manganese(iii)
- dual-mode epr
- high-frequency
- iron corroles
- structural-characterization
- noninnocent ligands
- porphyrin complexes
- oxidation-states
- spectroscopy
Publication and Content Type
- ref (subject category)
- art (subject category)
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