High-Valent Manganese-Oxo Valence Tautomers and the Influence of Lewis/Bronsted Acids on C-H Bond Cleavage.

ABSTRACT: The addition of Lewis or Brönsted acids (LA = Zn(OTf)₂, B(C₆F₅)₃, HBAr^F, TFA) to the high-valent manganese-oxo complex Mn^V(O)(TBP₈Cz) results in the stabilization of a valence tautomer Mn^IV(O-LA)(TBP₈Cz^•+). The Zn^II 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-N_ave = 1.89 Å and a fifth N/O ligand at 1.61 Å, corresponding to the terminal ox

SUBMITTER: Baglia RA 

PROVIDER: S-EPMC5228481 | biostudies-literature | 2016 Oct

REPOSITORIES: biostudies-literature