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A stable manganese(V)-oxo corrolazine complex.

Beaven S Mandimutsira1, Bobby Ramdhanie, Ryan C Todd

  • 1Department of Chemistry, The Johns Hopkins University, Baltimore, Maryland 21218, USA.

Journal of the American Chemical Society
|December 19, 2002
PubMed
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Researchers report a stable oxomanganese(V) corrolazine, a high-valent complex synthesized at room temperature. This breakthrough offers a new avenue for studying reactive manganese species in porphyrinoid chemistry.

Area of Science:

  • Inorganic Chemistry
  • Organometallic Chemistry
  • Coordination Chemistry

Background:

  • High-valent metal-oxo species are crucial in various catalytic oxidation reactions.
  • Isolation and characterization of stable high-valent porphyrinoid complexes remain challenging.
  • Manganese-corrolazine complexes offer a unique platform for exploring unusual oxidation states.

Purpose of the Study:

  • To synthesize and characterize a stable oxomanganese(V) corrolazine complex.
  • To investigate the structural and spectroscopic properties of this novel high-valent species.
  • To explore the reactivity of the oxomanganese(V) complex in ligand transfer reactions.

Main Methods:

  • Stoichiometric reaction of manganese(III) corrolazine with m-CPBA.

Related Experiment Videos

  • Purification using silica gel chromatography at room temperature.
  • Characterization by 1H NMR, LDI-TOFMS, and resonance Raman spectroscopy.
  • Isotopic labeling studies with H218O.
  • Reactivity studies involving oxo ligand transfer to triphenylphosphine (PPh3).

    • Main Results:

    • Successful synthesis and isolation of a stable oxomanganese(V) corrolazine, (TBP)8(Cz)Mn(V)O (2), at room temperature.
    • Diamagnetic 1H NMR spectrum confirmed a low-spin d2 Mn(V)O species.
    • Mass spectrometry confirmed the molecular weight and isotopic labeling.
    • Resonance Raman spectroscopy showed a characteristic Mn-oxo bond stretch at 979 cm-1 (16O) and 938 cm-1 (18O).
    • The complex readily transferred its oxo ligand to PPh3, reducing back to the Mn(III) state.

    Conclusions:

    • The reported oxomanganese(V) corrolazine is the first isolable at room temperature.
    • This stable complex provides a valuable tool for studying high-valent manganese chemistry.
    • The findings open new possibilities for designing catalysts based on stable high-valent porphyrinoid complexes.