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Addition of an anionic donor to an Mn V (O) porphyrinoid complex causes a dramatic increase in 2‐electron oxygen‐atom‐transfer (OAT) chemistry. The 6‐coordinate [Mn V (O)(TBP 8 Cz)(CN)] −  was generated from addition of Bu 4 N + CN −  to the 5‐coordinate Mn V (O) precursor. The cyanide‐ligated complex was characterized for the first time by Mn K‐edge X‐ray absorption spectroscopy (XAS) and gives MnO=1.53 Å, MnCN=2.21 Å. In combination with computational studies these distances were shown to correlate with a singlet ground state. Reaction of the CN −  complex with thioethers results in OAT to give the corresponding sulfoxide and a 2e − ‐reduced Mn III (CN) −  complex. Kinetic measurements reveal a dramatic rate enhancement for OAT of approximately 24 000‐fold versus the same reaction for the parent 5‐coordinate complex. An Eyring analysis gives Δ H  ≠ =14 kcal mol −1 , Δ S  ≠ =−10 cal mol −1  K −1 . Computational studies fully support the structures, spin states, and relative reactivity of the 5‐ and 6‐coordinate Mn V (O) complexes.

Dramatic Influence of an Anionic Donor on the Oxygen‐Atom Transfer Reactivity of a Mn V –Oxo Complex