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Investigating Superoxide Transfer through a mu-1,2-O-2 Bridge between Nonheme Ni-III-Peroxo and Mn-II Species by DFT Methods to Bridge Theoretical and Experimental Views
- Investigating Superoxide Transfer through a mu-1,2-O-2 Bridge between Nonheme Ni-III-Peroxo and Mn-II Species by DFT Methods to Bridge Theoretical and Experimental Views
- Cho, KB[Cho, Kyung-Bin]; Cho, J[Cho, Jaeheung]; Shaik, S[Shaik, Sason]; Nam, W[Nam, Wonwoo]
- DGIST Authors
- Cho, J[Cho, Jaeheung]
- Issue Date
- Journal of Physical Chemistry Letters, 5(14), 2437-2442
- Article Type
- Biomimetic Model; Density Functional Theory; Dioxygen Transfer; Dioxygens; Fast Reaction; Intermediate Structures; Manganese; Metal-Oxygen Intermediate; Nickel; Oxygen; Peroxocomplexes; Reaction Intermediates; Reaction Mechanism; Transfer Reaction
- Previously, a fast unprecedented O2 •- transfer reaction has been observed experimentally when adding a MnII complex into a solution containing a NiIII-peroxo complex. Due to the fast reaction rate, no intermediates were observed. We have investigated this reaction with density functional theory (DFT) and show that DFT is unusually problematic in reproducing the correct spin state for the investigated Ni III-peroxo complex, something which calls for examination of all previous Ni-dioxygen studies. Surprisingly, the BP86 functional is shown to yield energies more in agreement with known experiments than B3LYP. The calculations reveal for the first time an intermediate structure in a complete O2 •- transfer reaction, shown here to be a short-lived bridging Ni-(μ-1,2-O2)-Mn structure. © 2014 American Chemical Society.
- American Chemical Society
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