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- W2069497275 abstract "The interaction of reduced transition-metal porphyrins [e.g. PMn (II), PFe (II), PCo (II)] with oxygen species (· O 2 ·, H 2 + O ·/ HO ·, HOO ·, · O ·) involves radical/radical coupling to form covalent bonds. Coordinately unsaturated iron(II) porphyrins form two sigma bonds with · O 2 ·(-Δ G BF = 1–6 kcal mol -1 ) via two of the four unpaired d-electrons of the iron center. The hydroxyl radical [Formula: see text] couples with an unpaired electron of the PM (II) porphyrins to form a single covalent bond [[Formula: see text], PM III – OH ]. The bond energies (-Δ G BF ) for [Formula: see text] and [Formula: see text] are 65 ± 4 and 58 kcal mol -1 , respectively. Under neutral conditions the uncharged species [( Cl 8 TPP ) Mn III – OH , ( Cl 8 TPP ) Fe III – OH , (Cl 8 TPP)Co III - OH ] have bond-formation energies (-Δ G BF ) of 70 ± 4, 63, and 61 kcal mol -1 , respectively. In acetonitrile solutions atomic oxygen (· O ·; derived from ozone, O 3 ) couples with ( Cl 8 TPP ) Mn III [ ClO 4 ], ( Cl 8 TPP ) Mn II , ( Cl 8 TPP ) Fe III [ ClO 4 ], and ( Cl 8 TPP ) Fe II to form ( Cl 8 TPP + ) Mn V O (-ΔG BF = 59 ± 4 kcal mol -1 ), ( Cl 8 TPP ) Mn IV = O (85 kcal mol -1 ), ( Cl 8 TPP + ·) Fe IV = O (68 kcal mol -1 ; model for compound I of horseradish peroxidase), and ( Cl 8 TPP ) Fe IV = O (78 kcal mol -1 ; model for compound II of horseradish peroxidase). The weakly bonded species [( Cl 8 TPP + ) Mn V = O and ( Cl 8 TPP + ·) Fe IV = O ] epoxidize olefins with near-stoichiometric efficiency; the other two species are essentially unreactive with olefins." @default.
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- W2069497275 title "The nature of the bonding between metalloporphyrins [<font>Fe(II)</font>, <font>Co(II)</font>, <font>Mn(II)</font>] and oxygen species (·<font>O</font><sub>2</sub>·, <font>H</font><sub>2</sub><sup>+</sup><font>O</font>·/<font>HO</font>·, <font>HOO</font>·, ·<font>O</font>·)" @default.
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- W2069497275 doi "https://doi.org/10.1002/jpp.559" @default.
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