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 Ph2 Fe(I)- and other low-valent ferrates are more reactive than Ph3 Fe(II)- ; Ph4 Fe(III)- is inert. The coordination of a PPh3 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 Ph2 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 Ph3 Fe(II)- .

Mössbauer and mass spectrometry support for iron(ii) catalysts in enantioselective C-H activation.

A combination of electrospray-ionization mass spectrometry and Mössbauer spectroscopy was used to investigate the species generated in situ in highly enantioselective Fe/NHC-catalyzed C-H alkylations. The findings indicate an organometallic iron(ii)-NHC species to be of key relevance in the asymmetric catalysis.