Hydrolysis, hydrosulfidolysis, and aminolysis of imido(methyl)rhenium complexes

Article abstract of DOI:10.1021/ic0000956

The tris(imido)methylrhenium complex CH₃Re(NAd)₃ (1a, Ad = 1-adamantyl) reacts with H₂O to give CH₃Re(NAd)₂O (2a) and AdNH₂. The resulting di(imido)oxo species can further react with another molecule of H₂O to generate CH₃Re(NAd)O₂ (3a). The kinetics of these reactions have been studied by means of ¹H NMR and UV-vis spectroscopies. The second-order rate constant for the reaction of 1a 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 (1b, 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(μ-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) A, b = 10.9766 (7) A, c = 18.1645 (11) A, β = 108.268(1)°, V = 5771.5 (6) β³, Z = 4. The reaction between CH₃Re(NAr)₂O (2b) and H²S also yields the dinuclear compound 4b. Unlike 1b, 1a reacts with aniline derivatives to give mixed imido rhenium complexes.