The synthesis and characterization of the first stable trialkyl(difluoroamino)silane, R3SiNF2, aswell as of R3SiNHF and R3SiN(CH3)F in moderate yields are reported. The (difluoroamino)silanehas promise as a new synthon for the introduction of the −NF2 group into a variety of electrophilicinorganic and organic substrates. Activation barriers and relative energies were calculated for theunimolecular decompositions of Me3SiCF3 and t-Bu3SiNF2 using density functional theory (B3LYP/6-31G*). The calculated activation energies confirm the long-assumed kinetic stability of Me3SiCF3.