N. W. Mitzel, A. J. Blake, D. Rankin
May 7, 1997
Citations
0
Influential Citations
66
Citations
Journal
Journal of the American Chemical Society
Abstract
Tetrakis(N,N-dimethylhydroxylamido)silane, Si(ONMe2)4 (1), and the analogous ethyl compound, Si(ONEt2)4 (2), have been prepared by the reaction of silicon tetrachloride with 4 equiv of the corresponding lithium N,N-dialkylhydroxylamide. The compounds have been characterized by elemental analysis, IR spectroscopy, NMR spectroscopy of the nuclei 1H, 13C, 15N [including the determination of 1J(29Si15N) coupling constants], 17O, and 29Si, and nominal and high-resolution mass spectrometry. A crystal structure determination on 1 showed the molecule to be (4 + 4)-coordinate with short Si···N contacts [2.514(3)−2.555(3) A] and narrow SiON angles [109.1° on average]. For comparison, the crystal structure of the isoelectronic Si(OCHMe2)4 (in situ grown crystal) was determined, showing the absence of β-donor interactions and an SiOC angle of 124.7(1)°. Ab initio calculations have been performed on the model compounds Si(ONH2)4 and H3SiONMe2 as well as the electronegatively substituted fluoro derivatives FH2SiONMe2 a...