Gallium Hydrides and O/N-Donors as Tunable Systems in C-F Bond Activation

Chemistry, an Asian Journal
Alma D JaegerDieter Lentz

Abstract

The gallium hydrides (iBu)2 GaH (1 a), LiGaH4 (1 b) and Me3 N⋅GaH3 (1 c) hydrodefluorinate vinylic and aromatic C-F bonds when O and N donor molecules are present. 1 b exhibits the highest reactivity. Quantitative conversion to the hydrodefluorination (HDF) products could be observed for hexafluoropropene and 1,1,3,3,3-pentafluoropropene, 94 % conversion of pentafluoropyridine and 49 % of octafluorotoluene. Whereas for the HDF with 1 b high conversions are observed when catalytic amounts of O donor molecules are added, for 1 a, the addition of N donor molecules lead to higher conversions. The E/Z selectivity of the HDF of 1,1,3,3,3-pentafluoropropene is donor-dependent. DFT studies show that HDF proceeds in this case via the gallium hydride dimer-donor species and a hydrometallation/elimination sequence. Selectivities are sensitive to the choice of donor, as the right donor can lead to an on/off switching during catalysis, that is, the hydrometallation step is accelerated by the presence of a donor, but the donor dissociates prior to elimination, allowing the inherently more selective donorless gallium systems to determine the selectivity.

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Citations

Jul 16, 2019·Journal of the American Chemical Society·Nicholas O AndrellaR Tom Baker
Aug 19, 2020·Chemical Reviews·Alexandre J Sicard, R Tom Baker
Aug 28, 2021·Chemical Reviews·Matthew M D RoyEric Rivard

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