Unravelling the Effect of Acid‐Driven Electron Transfer in High‐Valent FeIV=O/MnIV=O Species and Its Implications for Reactivity

Abstract

AbstractThe electron transfer (ET) step is one of the crucial processes in biochemical redox reactions that occur in nature and has been established as a key step in dictating the reactivity of high‐valent metal‐oxo species. Although metalloenzymes possessing metal‐oxo units at their active site are typically associated with outer‐sphere electron transfer (OSET) processes, biomimetic models, in contrast, have been found to manifest either an inner‐sphere electron transfer (ISET) or OSET mechanism. This distinction is clearly illustrated through the behaviour of [(N4Py)MnIV(O)]2+ (1) and [(N4Py)FeIV(O)]2+ (2) complexes, where complex 1 showcases an OSET mechanism, while complex 2 exhibits an ISET mechanism, especially evident in their reactions involving C−H bond activation and oxygen atom transfer reactions in the presence of a Lewis/Bronsted acid. However, the precise reason for this puzzling difference remains elusive. This work unveils the origin of the perplexing inner‐sphere vs outer‐sphere electron transfer process (ISET vs OSET) in [(N4Py)MnIV(O)]2+ (1) and [(N4Py)FeIV(O)]2+ (2) species in the presence of Bronsted acid. The calculations indicate that when the substrate (toluene) approaches both 1 and 2 that is hydrogen bonded with two HOTf molecules (denoted as 1‐HOTf and 2‐HOTf, respectively), proton transfer from one of the HOTf molecules to the metal‐oxo unit is triggered and a simultaneous electron transfer occurs from toluene to the metal centre. Interestingly, the preference for OSET by 1‐HOTf is found to originate from the choice of MnIV=O centre to abstract spin‐down (β) electron from toluene to its δ(dxy) orbital. On the other hand, in 2‐HOTf, a spin state inversion from triplet to quintet state takes place during the proton (from HOTf) coupled electron transfer (from toluene) preferring a spin‐up (α) electron abstraction to its σ*(dz2) orbital mediated by HOTf giving rise to ISET. In addition, 2‐HOTf was calculated to possess a larger reorganisation energy, which facilitates the ISET process via the acid. The absence of spin‐inversion and smaller reorganisation energy switch the mechanism to OSET for 1‐HOTf. Therefore, for the first time, the significance of spin‐state and spin‐inversion in the electron transfer process has been identified and demonstrated within the realm of high‐valent metal‐oxo chemistry. This discovery holds implications for the potential involvement of high‐valent Mn‐oxo species in performing similar transformative processes within Photosystem II.