8 research outputs found
Oxygen-atom transfer reactivity of axially ligated Mn(V)âoxo complexes: Evidence for enhanced electrophilic and nucleophilic pathways
Addition of anionic donors to the manganese(V)âoxo corrolazine complex MnV(O)(TBP8Cz) has a dramatic influence on oxygen-atom transfer (OAT) reactivity with thioether substrates. The sixcoordinate anionic [MnV(O)(TBP8Cz)(X)]â complexes (X = Fâ, N3â, OCNâ) exhibit a âŒ5 cmâ1 downshift of the MnâO vibrational mode relative to the parent MnV(O)(TBP8Cz) complex as seen by resonance Raman spectroscopy. Product analysis shows that the oxidation of thioether substrates gives sulfoxide product, consistent with single OAT. A wide range of OAT reactivity is seen for the different axial ligands, with the following trend determined from a comparison of their second-order rate constants for sulfoxidation: five-coordinate â thiocyanate â nitrate < cyanate < azide < fluoride âȘ cyanide. This trend correlates with DFT calculations on the binding of the axial donors to the parent MnV(O)(TBP8Cz) complex. A Hammett study was performed with p-X-C6H4SCH3 derivatives and [MnV(O)(TBP8Cz)(X)]â(X = CNâ or Fâ) as the oxidant, and unusual âV-shapedâ Hammett plots were obtained. These results are rationalized based upon a change in mechanism that hinges on the ability of the [MnV(O)(TBP8Cz)(X)]â complexes to function as either an electrophilic or weak nucleophilic oxidant depending upon the nature of the para-X substituents. For comparison, the oneelectron-oxidized cationic MnV(O)(TBP8Czâą+) complex yielded a linear Hammett relationship for all substrates (Ï = â1.40), consistent with a straightforward electrophilic mechanism. This study provides new, fundamental insights regarding the influence of axial donors on high-valent MnV(O) porphyrinoid complexes