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 language | English |
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Pages (from-to) | 10700-10708 |
Number of pages | 9 |
Journal | Journal of the American Chemical Society |
Volume | 143 |
Issue number | 28 |
Early online date | 12 Jul 2021 |
DOIs | |
Publication status | Published - 21 Jul 2021 |
ASJC Scopus subject areas
- Catalysis
- General Chemistry
- Biochemistry
- Colloid and Surface Chemistry