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Title: Tuning the reactivity of mononuclear nonheme manganese(iv)-oxo complexes by triflic acid

Journal Article · · Chemical Science
DOI:https://doi.org/10.1039/C5SC00535C· OSTI ID:1215397
 [1];  [2];  [1];  [1];  [3];  [4];  [1]
  1. Ewha Womans Univ., Seoul (Korea)
  2. Osaka Univ., Suita (Japan). Graduate School of Engineering.
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  4. Ewha Womans Univ., Seoul (Korea); Osaka Univ., Suita (Japan). Graduate School of Engineering.

Triflic acid (HOTf)-bound nonheme Mn(IV)-oxo complexes, [(L)MnIV(O)]2+–(HOTf)2 (L = N4Py and Bn-TPEN; N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine and Bn-TPEN = N-benzyl-N,N',N'-tris(2-pyridylmethyl)ethane-1,2-diamine), were synthesized by adding HOTf to the solutions of the [(L)MnIV(O)]2+ complexes and were characterized by various spectroscopies. The one-electron reduction potentials of the MnIV(O) complexes exhibited a significant positive shift upon binding of HOTf. The driving force dependences of electron transfer (ET) from electron donors to the MnIV(O) and MnIV(O)–(HOTf)2 complexes were examined and evaluated in light of the Marcus theory of ET to determine the reorganization energies of ET. The smaller reorganization energies and much more positive reduction potentials of the [(L)MnIV(O)]2+–(HOTf)2 complexes resulted in greatly enhanced oxidation capacity towards one-electron reductants and para-X-substituted-thioanisoles. The reactivities of the Mn(IV)-oxo complexes were markedly enhanced by binding of HOTf, such as a 6.4 × 105-fold increase in the oxygen atom transfer (OAT) reaction (i.e., sulfoxidation). Such a remarkable acceleration in the OAT reaction results from the enhancement of ET from para-X-substituted-thioanisoles to the MnIV(O) complexes as revealed by the unified ET driving force dependence of the rate constants of OAT and ET reactions of [(L)MnIV(O)]2+–(HOTf)2. In contrast, deceleration was observed in the rate of H-atom transfer (HAT) reaction of [(L)MnIV(O)]2+–(HOTf)2 complexes with 1,4-cyclohexadiene as compared with those of the [(L)MnIV(O)]2+ complexes. Thus, the binding of two HOTf molecules to the MnIV(O) moiety resulted in remarkable acceleration of the ET rate when the ET is thermodynamically feasible. When the ET reaction is highly endergonic, the rate of the HAT reaction is decelerated due to the steric effect of the counter anion of HOTf.

Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC)
Grant/Contract Number:
AC03-76SF00515
OSTI ID:
1215397
Journal Information:
Chemical Science, Vol. 6, Issue 6; ISSN 2041-6520
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 75 works
Citation information provided by
Web of Science

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Structure and Unprecedented Reactivity of a Mononuclear Nonheme Cobalt(III) Iodosylbenzene Complex journal May 2020