The origins of dramatic axial ligand effects: Closed-shell Mn VO complexes use exchange-enhanced open-shell states to mediate efficient H abstraction reactions

Deepa Janardanan*, Dandamudi Usharani, Sason Shaik

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

41 Scopus citations

Abstract

Spin-state effects: In [(Cz)Mn VO] complexes, even with singlet closed-shell ground states, the reactive state is the open-shell triplet B state (S B=1) that has a high oxyl radical character and a transition state (TS) stabilized by exchange-enhanced reactivity (EER; see picture). The dramatic axial ligand effect originates in the EER of this state.

Original languageEnglish
Pages (from-to)4421-4425
Number of pages5
JournalAngewandte Chemie - International Edition
Volume51
Issue number18
DOIs
StatePublished - 27 Apr 2012

Keywords

  • density functional calculations
  • exchange-enhanced reactivity
  • high-valent Mn-oxo
  • hydrogen atom abstraction

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