Synthesis and molecular structures of N,N-dimethylhydroxylamino-trichlorosilane and -germane †

Abstract

The compounds Cl₃SiONMe₂ and Cl₃GeONMe₂ have been prepared by reacting HONMe₂ with SiCl₄ and GeCl₄, respectively, in the presence of the auxiliary base 2,6-dimethylpyridine. Their identity was proven by gas-phase IR and solution NMR spectroscopy of the nuclei ¹H, ¹³C, ¹⁵N, ¹⁷O, ²⁹Si, by mass spectrometry and elemental analyses. The solid-state structure of Cl₃SiONMe₂ was determined by low-temperature X-ray crystallography. The molecular structures of Cl₃SiONMe₂ and Cl₃GeONMe₂ in the gas phase have been determined by analysis of electron diffraction data augmented by restraints derived from ab initio calculations (MP2/6-31G*). The molecules adopt C_s symmetry. Important gas-phase geometry parameter values for Cl₃SiONMe₂ are: Si–O 1.623(3), Si–Cl_in-plane 2.022(4), Si–Cl_out-of-plane 2.024(2), O–N 1.479(6) Å, Si–O–N 105.6(8), O–Si–Cl_in-plane 104.2(3), O–Si–Cl_out-of-plane 113.7(2)°, for Cl₃GeONMe₂: Ge–O 1.759(6), Ge–Cl_in-plane 2.104(4), Ge–Cl_out-of-plane 2.106(2), O–N 1.484(9) Å, Ge–O–N 104.0(11), O–Ge–Cl_in-plane 108.9(20), O–Ge–Cl_out-of-plane 111.6(12)°. The structural data are interpreted in terms of weak attractive interactions between the nitrogen donor and the silicon/germanium acceptor atoms. The results are discussed in comparison with other structural data from the literature: the donor–acceptor interaction in Cl₃SiONMe₂ is weaker than those in H₃SiONMe₂ or ClH₂SiONMe₂, but stronger than that in Me₃SiON(CF₃)₂. Both compounds reveal stronger donor–acceptor interactions than the methyl analogues Me₃SiONMe₂.

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