Synthesis, characterization and theoretical calculations of model compounds of silanols catalyzed by TEMPO to elucidate the presence of Si–O–Si and Si–O–N bonds

We report the results from the reactions of 1-phenylethanol, 2-methylpropanol, trimethylsilanol and triphenylsilanol with TEMPO, OH-TEMPO and Br-TEMPO salt at different reaction conditions to obtain model functionalized compounds. With 1-phenylethanol, the ketone compound was obtained as expected, but when using triphenylsilanol the corresponding hexaphenyldisiloxane [di(triphenylsilane)ether] was obtained in crystal form, as well as the silaneoxiamine (Si–O–N). The hexaphenyldisiloxane crystal belonged to the triclinic crystal system with a space group P, a = 8.5829(4) A, b = 9.4856(4) A, c = 10.9694(5) A, α = 95.951(4)°, β = 90.059(3)°, γ = 113.352(4)°, the asymmetric unit comprised of Z = 1. The results showed that the synthetic method to obtain silane ether is simple and can be completed in one step, as well as independently of the type of TEMPO and base used. Also, under the same reactions conditions, we prepared the corresponding TEMPO-containing silanes as triphenylsilaneoxiamine and observed formation of Si-oxide chains through an in situ polycondensation reaction. The resulting compounds were characterized by FT-IR spectroscopy, mass spectrometry (EI), and 1H-NMR. The best assignment for infrared spectroscopy characterization and the structural parameters by vibrational frequencies were determined by DFT calculations.