The tris(imido)methylrhenium complex CH3Re(NAd)(3) (1a, Ad = 1-adamantyl) reacts with H2O to give CH3Re-(NAd)(2)O (2a) and AdNH(2). The resulting di(imido)oxo species can further react with another molecule of H2O to generate CH3Re(NAd)O-2 (3a). The kinetics of these reactions have been studied by means of H-1 NMR and UV-vis spectroscopies. The second-order rate constant for the reaction of la with H2O at 298 K in C6H6 is 3.3 L mol(-1) s(-1), which is much larger than the value 1 x 10(-4) L mol(-1) s(-1) obtained for the reaction between CH3Re(NAr)(3) (1, Ar = 2,6-diisopropylphenyl) and H2O in CH3CN at 313 K. Both 1a and 1b react with H2S to produce the rhenium(VII) sulfide, (CH3Re(NR)(2))(2)(mu-S)(2) (4a, R = Ad; 4b, R = Ar), with second-order rate constants of 17 and 1.6 x 10(-4) L mol(-1) s(-1) in C6H6 and CH3CN, respectively. Complex 4b has been structurally characterized. The crystal data are as follows: space group C2/c, a = 30.4831 (19) Angstrom, b = 10.9766 (7) Angstrom, c = 18.1645 (11)Angstrom, beta = 108.268(1)degrees, V = 5771.5 (6) Angstrom(3), Z = 4. The reaction between CH3Re(NAr)(2)O (2b) and H2S also yields the dinuclear compound 4b. Unlike Ib, la reacts with aniline derivatives to give mixed imido rhenium complexes.