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• W2525567643 endingPage "10809" @default.
• W2525567643 startingPage "10800" @default.
• W2525567643 abstract "The addition of Lewis or Brönsted acids (LA = Zn(OTf)2, B(C6F5)3, HBArF, TFA) to the high-valent manganese-oxo complex MnV(O)(TBP8Cz) results in the stabilization of a valence tautomer MnIV(O-LA)(TBP8Cz•+). The ZnII and B(C6F5)3 complexes were characterized by manganese K-edge X-ray absorption spectroscopy (XAS). The position of the edge energies and the intensities of the pre-edge (1s to 3d) peaks confirm that the Mn ion is in the +4 oxidation state. Fitting of the extended X-ray absorption fine structure (EXAFS) region reveals 4 N/O ligands at Mn-Nave = 1.89 Å and a fifth N/O ligand at 1.61 Å, corresponding to the terminal oxo ligand. This Mn-O bond length is elongated compared to the MnV(O) starting material (Mn-O = 1.55 Å). The reactivity of MnIV(O-LA)(TBP8Cz•+) toward C-H substrates was examined, and it was found that H• abstraction from C-H bonds occurs in a 1:1 stoichiometry, giving a MnIV complex and the dehydrogenated organic product. The rates of C-H cleavage are accelerated for the MnIV(O-LA)(TBP8Cz•+) valence tautomer as compared to the MnV(O) valence tautomer when LA = ZnII, B(C6F5)3, and HBArF, whereas for LA = TFA, the C-H cleavage rate is slightly slower than when compared to MnV(O). A large, nonclassical kinetic isotope effect of kH/kD = 25-27 was observed for LA = B(C6F5)3 and HBArF, indicating that H-atom transfer (HAT) is the rate-limiting step in the C-H cleavage reaction and implicating a potential tunneling mechanism for HAT. The reactivity of MnIV(O-LA)(TBP8Cz•+) toward C-H bonds depends on the strength of the Lewis acid. The HAT reactivity is compared with the analogous corrole complex MnIV(O-H)(tpfc•+) recently reported (J. Am. Chem. Soc. 2015, 137, 14481-14487)." @default.
• W2525567643 created "2016-10-07" @default.
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• W2525567643 date "2016-09-30" @default.
• W2525567643 modified "2023-09-24" @default.
• W2525567643 title "High-Valent Manganese–Oxo Valence Tautomers and the Influence of Lewis/Brönsted Acids on C–H Bond Cleavage" @default.
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• W2525567643 doi "https://doi.org/10.1021/acs.inorgchem.6b02109" @default.
• W2525567643 hasPubMedCentralId "https://www.ncbi.nlm.nih.gov/pmc/articles/5228481" @default.
• W2525567643 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/27689821" @default.
• W2525567643 hasPublicationYear "2016" @default.
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