Investigating superoxide transfer through a μ-1,2-O2 bridge between nonheme NiIII-peroxo and MnII species by DFT methods to bridge theoretical and experimental views

Kyung Bin Cho, Jaeheung Cho, Sason Shaik, Wonwoo Nam

Research output: Contribution to journalArticlepeer-review

6 Scopus citations

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.

Original languageEnglish
Pages (from-to)2437-2442
Number of pages6
JournalJournal of Physical Chemistry Letters
Volume5
Issue number14
DOIs
StatePublished - 17 Jul 2014

Keywords

  • biomimetic model
  • density functional theory
  • dioxygen transfer
  • metal-oxygen intermediate
  • reaction mechanism

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