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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

Title
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
Authors
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
2014-07-17
Citation
Journal of Physical Chemistry Letters, 5(14), 2437-2442
Type
Article
Article Type
Article
Keywords
Biomimetic ModelDensity Functional TheoryDioxygen TransferDioxygensFast ReactionIntermediate StructuresManganeseMetal-Oxygen IntermediateNickelOxygenPeroxocomplexesReaction IntermediatesReaction MechanismTransfer Reaction
ISSN
1948-7185
Abstract
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.
URI
http://hdl.handle.net/20.500.11750/3071
DOI
10.1021/jz501193k
Publisher
American Chemical Society
Files:
There are no files associated with this item.
Collection:
Emerging Materials ScienceETC1. Journal Articles


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