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• W2034265417 startingPage "12416" @default.
• W2034265417 abstract "The relatively stable oxoMn(V) porphyrins generated by oxidation of Mn(III) porphyrins in alkaline solutions using peroxides are unambiguously identified as trans-dioxo species. Raman spectra revealed symmetric OMnVO stretching frequencies between 741 and 744 cm-1 for five porphyrin complexes while the IR of dioxo-MnV-tetrapentafluoroporphyrin [MnV(O2)(TPFPP)]- displayed an antisymmetric stretch at 805 cm-1. Both half-labeled and fully labeled 18O−MnV porphyrin complexes were prepared, and the Raman and IR shifts correspond well with a linear, three-body OMnO oscillator model. Terminal, monooxo formulations such as HO−MnVO or five-coordinate MnVO are excluded by the data. The 1H NMR spectrum of [MnV(O2)(TMP)]-, which shows a single, sharp resonance for the two ortho methyl groups, is also consistent with octahedral coordination of D4h symmetry. The force constant F for the MnO double bond was calculated to be 454 N/m with a stretch−stretch force constant k = 67.2 N/m. Comparison with other Mn−O force constants revealed a very good agreement with Badger's rule spanning five Mn oxidation states. These dioxo-MnV porphyrins were shown to not exchange the oxo oxygens with bulk water solvent. Dioxo MnV porphyrins, which are anionic species [Por-MnV(O)2]-, are unreactive toward olefins in the presence of excess base but efficiently epoxidize cyclooctene upon protonation at −70 °C. These compounds are the only trans-dioxomanganese complexes of any type to be characterized as such, thus extending the known π-bonding arrangements for first-row transition metals." @default.
• W2034265417 created "2016-06-24" @default.
• W2034265417 creator A5001622149 @default.
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• W2034265417 date "2007-09-21" @default.
• W2034265417 modified "2023-10-18" @default.
• W2034265417 title "Trans-dioxo Manganese(V) Porphyrins" @default.
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• W2034265417 doi "https://doi.org/10.1021/ja0761737" @default.
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