Unprecedented Rate Enhancements of Hydrogen-Atom Transfer to a Manganese(V)–Oxo Corrolazine Complex


  • Funding was provided by the NSF (CHE0909587) (D.P.G.) and the Cleio Greer Fellowship (K.A.P.). Financial support for the purchase of the Bruker AutoFlex III MALDI-ToF mass spectrometer was provided by the NSF (CHE-0840463). The National Service of Computational Chemistry Software (NSCCS) is thanked for providing CPU time for the calculations.


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Runaway reactivity: A manganese(V)–oxo porphyrinoid complex displays an unprecedented increase in reaction rate for a hydrogen-atom abstraction upon addition of anionic axial ligands (X=F and CN; see scheme). Density functional theory calculations are in excellent agreement with experiment, and provide insight into the origins of these remarkable axial ligand effects.