Lithium fluoroarylamidinates [(ArFC(NSiMe3)(2)Li)(n).xD] (Ar-F = 4-CF3C6H4, n = 2, D = OEt2, X = 1 (2a); n = 1, D = TMEDA, x = 1 (4a); ArF = 2-FC6H4, n = 2, D = OEt2, X = 1 (2b); ArF = 4-FC6H4, n = 2, D = OEt2, X = 2 (2c); ArF = 2,6-F2C6H3, n = 2, D = OEt2 X = 1 (2d); n = 2, D = 2,6-F2C6H3CN, x = 2 (3d); Ar-F = C6F5, n = 2, D = OEt2, X = 1 (2e), n = 1, D = TMEDA, x = I (4e); n = 1, x = 2. D = OEt2 (5e): D = THF (6e)) were prepared by the well-known method from LiN(SiMe3)(2) and the corresponding nitrile in diethyl ether or by addition of the appropriate donor D to the respective diethyl ether complexes, Depending on the substituents at the aryl group and on the donors D, three different types of structures were confirmed by X-ray crystallography. Hydrolysis of 2e gave C6F5C(NSiMe3)N(H)SiMe3 (7e) and C6F5C(NH)N(H)SiMe3 (8e), The lithium fluoroarylamidinates 2a-2d react with Me3SiCl to give the corresponding tris(trimethylsilyl)fluoroarylamidines ArFC(NSiMe3)N(SiMe3)(2) (9a-9d). Attempts to prepare C6F5C(NSiMe3)N(SiMe3)(2) from 2e and Me3SiCl failed; however, the unprecedented cage {[C6F5C(NSiMe3)(2)Li](4)LiF} (10e) in which a fluoride center is surrounded by a distorted trigonal bipyramid of five Li atoms was obtained from this reaction.