Hydrogenolytic ring cleavage of gem-difluorocyclopropanes, e.g. I and II, occurs exclusively at the carbon-carbon bond opposite to the halogen-bearing center and affords mainly gem-difluoroalkanes, e.g. MeCH2CF2(CH2)3Me and III, resp. The intermediacy of catalyst/cyclopropane derived adducts (e.g., palladacyclobutanes or 1,3-dipalladiopropanes) is postulated in order to rationalize the formation of monofluorinated and halogen-free byproducts and, in addn., to explain specific substituent effects on the reaction rates. [on SciFinder (R)]