Three-Membered Ring or Open Chain Molecule − (F3C)F2SiONMe2a Model for the α-Effect in Silicon Chemistry
Citations Over TimeTop 23% of 2005 papers
Abstract
(F3C)F2SiONMe2 was prepared from LiONMe2 and F3CSiF3. It was characterized by gas IR and multinuclear solution NMR spectroscopy and by mass spectrometry. Its structure was elucidated by single crystal X-ray crystallography and by gas electron diffraction. (It exists as a conformer mixture.) Important findings were extremely acute SiON angles [solid 74.1(1) degrees , gas anti 84.4(32) degrees and gauche 87.8(20) degrees] and short Si...N distances [solid 1.904(2) A]. The bending potential of the SiON unit was calculated at the MP2/6-311++G(3df,2dp) level of theory and appears very flat and highly asymmetric. The calculated atomic charges (NPA) are counterintuitive to the expected behavior for a classical Si-N dative bond, as upon formation of the Si...N bond electron density is transferred mainly from oxygen to nitrogen, while the silicon charge is almost unaffected. Despite the molecular topology of a three-membered ring, the topology of the electron density shows neither a bond critical point between Si and N atoms nor a ring critical point, but the electron density and Laplacian values are related to other hypercoordinate Si compounds. The electronic properties of (F3C)F2SiONMe2 were compared to those of the adduct (F3C)F2(MeO)Si-NMe3, whose properties and structure were also calculated. The charge distribution and Laplacian values along the Si-N vectors in both molecules are similar but not equivalent. (F3C)F2SiONMe2 contains thus a nonclassical Si...N bond, and its properties can be regarded as a new model for the explanation of the old postulate of an alpha-effect in silicon chemistry, explaining the behavior of compounds with geminal Si and N atoms.
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