Mn(V)(O) versus Cr(V)(O) Porphyrinoid Complexes: Structural Characterization and Implications for Basicity Controlling H-Atom Abstraction

J Am Chem Soc. 2015 Sep 2;137(34):10874-7. doi: 10.1021/jacs.5b05142. Epub 2015 Aug 21.

Abstract

Isomorphous crystals of Mn(V)(O) and Cr(V)(O) corrolazines were characterized by single crystal X-ray diffraction. Reactivity studies with H atom donors and separated PCET reagents show a dramatic difference in H atom abstracting abilities for these two complexes. The implied large difference in driving force is opposite the trend in redox potentials, indicating that basicity is a key factor in determining the striking difference in reactivity for two metal-oxo species in identical ligand environments.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, Non-U.S. Gov't

MeSH terms

  • Chromium / chemistry*
  • Manganese / chemistry*
  • Metalloporphyrins / chemistry
  • Molecular Structure
  • Organometallic Compounds / chemical synthesis
  • Organometallic Compounds / chemistry*
  • Oxygen / chemistry*

Substances

  • Metalloporphyrins
  • Organometallic Compounds
  • corrolazine
  • Chromium
  • Manganese
  • Oxygen