Functionalization reactions of the refrigerants HFO-1234yf (2,3,3,3-tetrafluoropropene) and HFO-1234ze (1,3,3,3-tetrafluoropropene) were developed. The selectivity and reactivity towards CF groups of C-F activation reactions can be controlled by employing either a germane or a silane as the hydrogen source. Unique transformations were designed to accomplish consecutive hydrogermylation and C-F activation steps. This allowed for an unprecedented transformation of an olefinic C-F bond into a C-H bond by heterogeneous catalysis. These reactions are catalyzed by nanoscopic aluminum chlorofluoride (ACF) under very mild conditions.

Catalytic C–F activations at Lewis-acidic amorphous aluminum chlorofluoride (ACF) with Et3GeH and Et3SiH for reaction pathway control are presented.

The germylium ions [GeR3]+ catalyze dehydrodefluorination reactions of fluorinated alkanes when germanes are used as hydrogen source.

Functionalization reactions of the refrigerants HFO‐1234yf (2,3,3,3‐tetrafluoropropene) and HFO‐1234ze (1,3,3,3‐tetrafluoropropene) were developed. The selectivity and reactivity towards CF3 groups of C−F activation reactions can be controlled by employing either a germane or a silane as the hydrogen source. Unique transformations were designed to accomplish consecutive hydrogermylation and C−F activation steps. This allowed for an unprecedented transformation of an olefinic C−F bond into a C−H bond by heterogeneous catalysis. These reactions are catalyzed by nanoscopic aluminum chlorofluoride (ACF) under very mild conditions.

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