N-Trifluoromethyl-N-perfluoroalkyldichlorocarbimides CF3(R(f))NN=CCl2 (R(f) = CF3, C2F5, C3F7 (1)) are chlorofluorinated with ClF to give stable chlorohydrazines CF3(R(f))NN(Cl)CF2Cl (R(f) = CF3 (2), C2F5, C3F7 (3)). Trimethylsilylation of 2 with Me(3)SiCl in a 1:1 molar ratio gives the silylhydrazine (CF3)2NN(SiMe(3))CF2Cl (4) with concomitant loss of chlorine. The hydrazines CF3(R(f))NN(Cl)CF2Cl (R(f) = CF3 (2), C2F5, C3F7 (3)) are converted into the respective N-trifluoromethyl-N-(perfluoroalkyl)difluorocarbimides CF3(R(f))NN=CF2 (R(f) = CF3, C2F5 (6), C3F7 (5)) with catalytic amounts of Me(3)SiCl. A chlorofluorocarbimide CF3(C2F5)NN=CFCl (7) is obtained when Me(3)SnCl is used as a catalyst with CF3(C2F5)NN(Cl)CF2Cl. Chlorofluorination of 6 gives CF3(C2F5)NN(Cl)CF3 (8). Reaction of 5 with SF5OCl forms the hydrazine CF3(C3F7)NN(Cl)CF2OSF5 (9). With (CF3)(2)NN=CF2, (CF3)(3)COCl reacts to give the hydrazine (CF3)(2)NN(Cl)CF2OC(CF3)(3) (10). Photolysis of 2 and 3 results in formation of the tetrazanes [CF3(R(f))NNCF2Cl](2) (R(f) = CF3 (11), C3F7 (12)), whereas the photolysis of 8 gives a perfluorinated tetrazane [CF3(C2F5)NNCF3](2) (13). Photolysis of the ether hydrazines 9 and 10 yields the first SF5-containing tetrazane [CF3(C3F7)NNCF2OSF5](2) (14) and [(CF3)(2)NNCF2OC(CF3)(3)](2) (15), respectively. Photolysis of 8 with cyanogen chloride allows the low yield preparation of a novel 3N-dichlorocarbimide CF3(C2F5)NN(CF3)N=CCl2 (16).