β-Donor Bonds in SiON Units: An Inherent Structure- Determining Property Leading to (4 + 4)-Coordination in Tetrakis-(N,N-dimethylhydroxylamido)silane

Tetrakis( N, N -dimethylhydroxylamido)silane, Si(ONMe 2 ) 4 ( 1 ), and the analogous ethyl compound, Si(ONEt 2 ) 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 1 H, 13 C, 15 N [including the determination of 1 J ( 29 Si 15 N) coupling constants], 17 O, and 29 Si, 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) Å] and narrow SiON angles [109.1° on average]. For comparison, the crystal structure of the isoelectronic Si(OCHMe 2 ) 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(ONH 2 ) 4 and H 3 SiONMe 2 as well as the electronegatively substituted fluoro derivatives FH 2 SiONMe 2 and F 3 SiONMe 2 up to the MP2/6-311G** level of theory. Si(ONH 2 ) 4 is predicted to adopt C 2 symmetry and to have an SiON angle of only 109.5°, while the interactions in the other model compounds are predicted to be much stronger, as indicated by their SiON angles: H 3 SiONMe 2 102.5°, FH 2 SiONMe 2 90.0°, and F 3 SiONMe 2 93.8°. The results are discussed with respect to the consequences of enlargement of the coordination sphere at the silicon atom, the unique chemical behavior of O -silylhydroxylamines (in particular their fast nucleophilic substitutions reactions), and the resulting use of this class of compounds in the silicone rubber industry.