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Title: High-valent manganese–oxo valence tautomers and the influence of Lewis/Brönsted acids on C–H bond cleavage

Journal Article · · Inorganic Chemistry
 [1];  [2];  [3];  [4];  [1]
  1. The Johns Hopkins Univ., Baltimore, MD (United States)
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  3. The Johns Hopkins Univ., Baltimore, MD (United States); Univ. of Wisconsin, Madison, WI (United States)
  4. The Johns Hopkins Univ., Baltimore, MD (United States); Chulalongkorn Univ., Bangkok (Thailand)
+ Show Author Affiliations

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. Furthermore, 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.

Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
USDOE
Grant/Contract Number:
AC02-76SF00515
OSTI ID:
1350592
Journal Information:
Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 20 Vol. 55; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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  • Peryshkov, Dmitry V.; Schrock, Richard R.; Takase, Michael K.
  • Journal of the American Chemical Society, Vol. 133, Issue 51, p. 20754-20757 https://doi.org/10.1021/ja210349m
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A High‐Valent Manganese(IV)–Oxo–Cerium(IV) Complex and Its Enhanced Oxidizing Reactivity journal September 2019
A High‐Valent Manganese(IV)–Oxo–Cerium(IV) Complex and Its Enhanced Oxidizing Reactivity journal November 2019
A Manganese(V)–Oxo Tetraamido Macrocyclic Ligand (TAML) Cation Radical Complex: Synthesis, Characterization, and Reactivity Studies journal November 2018
Interaction of Metal Oxido Compounds with B(C 6 F 5 ) 3 journal February 2019
Synthetic High-Valent M-O-X Oxidants: Synthetic High-Valent M-O-X Oxidants journal January 2018
meso-N-Methylation of a porphyrinoid complex: activating the H-atom transfer capability of an inert Re V (O) corrolazine journal January 2017
C–H activation and nucleophilic substitution in a photochemically generated high valent iron complex journal January 2018

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