LAUSR

Highly reactive organometallic species that mediate reductive proton-coupled electron transfer (PCET) reactions are an exciting area for development in catalysis, where a key objective focuses on tuning the reactivity of such species. This work pursues ligand-induced activation of a stable organometallic complex toward PCET reactivity. This is studied via the conversion of a prototypical Cp*FeIII-H species, [FeIII(η5-Cp*)(dppe)H]+ (Cp* = C5Me5-, dppe = 1,2-bis(diphenylphosphino)ethane), to a highly reactive, S = 1/2 ring-protonated endo-Cp*H-Fe relative, triggered by the addition of CO. Our assignment of the latter ring-protonated species contrasts with its previous reported formulation, which instead assigned it as a hypervalent 19-electron hydride, [FeIII(η5-Cp*)(dppe)(CO)H]+. Herein, pulse EPR spectroscopy (1,2H HYSCORE, ENDOR) and X-ray crystallography, with corresponding DFT studies, cement its assignment as the ring-protonated isomer, [FeI(endo-η4-Cp*H)(dppe)(CO)]+. A less sterically shielded and hence more reactive exo-isomer can be generated through oxidation of a stable Fe0(exo-η4-Cp*H)(dppe)(CO) precursor. Both endo- and exo-ring-protonated isomers are calculated to have an exceptionally low bond dissociation free energy (BDFEC-H ≈ 29 kcal mol-1 and 25 kcal mol-1, respectively) cf. BDFEFe-H of 56 kcal mol-1 for [FeIII(η5-Cp*)(dppe)H]+. These weak C-H bonds are shown to undergo proton-coupled electron transfer (PCET) to azobenzene to generate diphenylhydrazine and the corresponding closed-shell [FeII(η5-Cp*)(dppe)CO]+ byproduct.