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 , (Cl8TPP)CoIII- 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.

中文翻译：

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金属卟啉 [Fe(II), Co(II), Mn(II)] 和氧 (·O2·, H2+O·/HO·, HOO·,·O·) 之间的键合性质

还原过渡金属卟啉 [例如 PMn (II), PFe (II), PCo (II)] 与氧的相互作用 (· O2·， H2+O·/HO·、HOO·、·O·)涉及自由基/自由基偶联以形成共价键。配位不饱和铁 (II) 卟啉与 · O 形成两个 σ 键2·(-ΔG高炉= 1–6 千卡摩尔-1) 通过铁中心的四个未配对的 d 电子中的两个。羟基自由基 [公式：见正文] 与 PM (II) 卟啉的一个未配对电子偶联形成一个共价键 [[公式：见正文]，PM三- 哦 ]。键能（-ΔG高炉) 对于 [公式：见正文] 和 [公式：见正文] 分别为 65 ± 4 和 58 kcal mol-1， 分别。在中性条件下，不带电的物质 [( Cl8TPP ) 锰三– 哦, ( 氯8TPP ) 铁三– 哦，（氯8TPP)公司三- OH ] 具有成键能 (-Δ G高炉) 70 ± 4、63 和 61 kcal mol-1， 分别。在乙腈溶液中原子氧（·O·；衍生自臭氧，O3) 与 ( Cl8TPP ) 锰三[二氧化氯4], ( 氯8TPP ) 锰二, ( 氯8TPP ) 铁三[二氧化氯4] 和 ( 氯8TPP ) 铁二形成（Cl8跨太平洋伙伴关系协定+) 锰五O (-ΔG高炉= 59 ± 4 千卡摩尔-1), ( 氯8TPP ) 锰四= O (85 千卡摩尔-1), ( 氯8跨太平洋伙伴关系协定+·) 铁四= O (68 kcal 摩尔-1; 辣根过氧化物酶化合物 I 模型）和（Cl8TPP ) 铁四= O (78 kcal 摩尔-1; 辣根过氧化物酶化合物 II 模型）。弱键物种 [( Cl8跨太平洋伙伴关系协定+) 锰五= O 和 ( 氯8跨太平洋伙伴关系协定+·) 铁四= O ] 以接近化学计量的效率环氧化烯烃；其他两种物质基本上不与烯烃反应。