Probing Hydrogen Atom Transfer at a Phosphorus(V) Oxide Bond Using a “Bulky Hydrogen Atom” Surrogate: Analogies to PCET

Recent computational studies suggest that the phosphate support in the commercial vanadium phosphate oxide (VPO) catalyst may play a critical role in initiating butane C–H bond activation through a mechanism termed reduction-coupled oxo activation (ROA) similar to proton-coupled electron transfer (PCET); however, no experimental evidence exists to support this mechanism. Herein, we present molecular model compounds, (Ph₂N)₃VN–P­(O)­Ar₂ (Ar = C₆F₅ (2a), Ph (2b)), which are reactive to both weak H atom donors and a Me₃Si^• (a “bulky hydrogen atom” surrogate) donor, 1,4-bis­(trimethylsilyl)­pyrazine. While the former reaction led to product decomposition, the latter resulted in the isolation of the reduced, silylated complexes (Ph₂N)₃V–NP­(OSiMe₃)­Ar₂ (3a/b). Detailed analyses of possible reaction pathways, involving the isolation and full characterization of potential stepwise square-scheme intermediates, as well as the determination of minimum experimentally and computationally derived thermochemical values, are described. We find that stepwise electron transfer (ET) + silylium transfer (ST) or concerted EST mechanisms are most likely. This study provides the first experimental evidence supporting a ROA mechanism and may inform future studies in homogeneous or heterogeneous C–H activation chemistry, as well as open up a possible new avenue for main group/transition metal cooperative redox reactivity.