One approach for a metal-mediated derivatization of fluorinated molecules is based on C−F activation reactions. In order to make C−F bond cleavage steps feasible other strong element−fluorine bonds such as Si−F bonds have to be formed, but the interplay between silicon and metal centers can be very diverse. At rhodium, highly reactive Rh(I)silyl complexes such as [Rh(H)2(SiPh3)(PEt3)3] or [Rh{Si(OEt)3}(PEt3)3] can serve as suitable tools to induce a C−F activation step. We will report on the reactivity of fluorinated propenes as well as the hydrofluorocarbon 1234yf. The conversions will be compared to these of [Rh(GePh3)(PEt3)3], [Rh(H)(PEt3)3] and [Rh(Bpin)(PEt3)3] (pin: pinacolato). Another spin-off consists of C-F activation reactions of the olefins at nanoscopic aluminum chlorofluoride (ACF), which resulted in hydrodefluorination, C-C coupling and germylation processes. The investigations involve an immobilisation of silanes or germanes at a Lewis-acidic surface to generate activated species, which then can induce bond-cleavage steps.

Activation of fluorinated olefins by synergistic action at metal and silicon centres

255th National Meeting (2018)

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