Alkali metal adducts of an iron(0) complex and their synergistic FLP-type activation of aliphatic C–X bonds

Hendrik Tinnerman, Simon Sung, Dániel Csókás, Zhi Hao Toh, Craig Fraser, Rowan Young

Research output: Contribution to journalArticlepeer-review

Abstract

We report the formation and full characterization of weak adducts between Li+ and Na+ cations and a neutral iron(0) complex, [Fe(CO)3(PMe3)2] (1), supported by weakly coordinating [BArF20] anions, [1·M][BArF20] (M = Li, Na). The adducts are found to synergistically activate aliphatic C–X bonds (X = F, Cl, Br, I, OMs, OTf), leading to the formation of iron(II) organyl compounds of the type [FeR(CO)3(PMe3)2][BArF20], of which several were isolated and fully characterized. Stoichiometric reactions with the resulting iron(II) organyl compounds show that this system can be utilized for homocoupling and cross-coupling reactions and the formation of new C–E bonds (E = C, H, O, N, S). Further, we utilize [1·M][BArF20] as a catalyst in a simple hydrodehalogenation reaction under mild conditions to showcase its potential use in catalytic reactions. Finally, the mechanism of activation is probed using DFT and kinetic experiments that reveal that the alkali metal and iron(0) center cooperate to cleave C–X via a mechanism closely related to intramolecular FLP activation.
Original languageEnglish
Pages (from-to)10700-10708
Number of pages9
JournalJournal of the American Chemical Society
Volume143
Issue number28
Early online date12 Jul 2021
DOIs
Publication statusPublished - 21 Jul 2021

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