A series of 21 secondary (alkyl)(trimethylsilyl)amines HNR(TMS) [R = n-propyl (1), i-propyl (2), n-butyl (3) i-butyl (4), s-butyl (5), tert-butyl (6), c-pentyl (7), n-pentyl (8), i-pentyl (9), 1-methylbutyl (10), 2-methylbutyl (11), 1-ethylpropyl (12), 1,2-dimethylpropyl. (13), tert-pentyl (14), phenyl (15), c-hexyl (16), n-hexyl (17), N,N-dimethyl-3-aminopropyl (18), benzyl (19), n-heptyl (20), 1,1,3,3-tert-butyl (21); TMS = Si(CH3)(3)] has been prepared and fully characterized by elemental analyses, multinuclear (LH, C-13, Si-29, N-14) NMR, IR, UV/vis, MS, and bailing point. A new method for determination of boiling points of milligram-size samples, based on DSC (differential scanning calorimetry), is described. Each amine has been converted to the corresponding zinc bis(amide) compound Zn[N(TMS)(R)](2) [R = n-propyl (22), i-propyl (23), n-butyl (24), i-butyl (25), s-butyl (26), tert-butyl (27), c-pentyl (28), n-pentyl (29), i-pentyl (30), 1-methylbutyl(31), 2-methylbutyl (32), 1-ethylpropyl (33), 1,2-dimethylpropyl (33)1 tert-pentyl (35), phenyl (36), c-hexyl (37), n-hexyl (38), N,N-dimethyl-3-aminopropyl (39, benzyl (40), n-heptyl (41, 1,1,3,3-tert-butyl (32); TMS = Si(CH3)(3)] and subsequently fully characterized by elemental analyses, multinuclear (H-1) C-13, Si-29,N-14) NMR, IR, UV/vis, MS, and TGA. The experimental IR has been compared to the computationally calculated one for compound 27. Observed trends in volatility of the compounds an discussed in the context of the dominant intermolecular forces present in the condensed phase.