Microscopic Reactivity of Phenylferrate Ions toward Organyl Halides

Despite its practical importance, organoiron chemistry remains poorly understood due to its mechanistic complexity. Here, we focus on the oxidative addition of organyl halides to phenylferrate anions in the gas phase. By mass‐selecting individual phenylferrate anions, we can determine the effect of the oxidation state, the ligation, and the nuclearity of the iron complex on its reactions with a series of organyl halides RX. We find that Ph(2)Fe(I)(−) and other low‐valent ferrates are more reactive than Ph(3)Fe(II)(−); Ph(4)Fe(III)(−) is inert. The coordination of a PPh(3) ligand or the presence of a second iron center lower the reactivity. Besides direct cross‐coupling reactions resulting in the formation of RPh, we also observe the abstraction of halogen atoms. This reaction channel shows the readiness of organoiron species to undergo radical‐type processes. Complementary DFT calculations afford further insight and rationalize the high reactivity of the Ph(2)Fe(I)(−) complex by the exothermicity of the oxidative addition and the low barriers associated with this reaction step. At the same time, they point to the importance of changes of the spin state in the reactions of Ph(3)Fe(II)(−).