The hierarchy of ab initio and DFT methods for describing an intramolecular non-covalent Si?N contact in the silicon compounds using electron diffraction geometries?

Physical Chemistry Chemical Physics Pub Date: 2021-01-04 DOI: 10.1039/D0CP05872F

Abstract

In the series of silatranes XSi(OCH2CH2)3N, 1 (X = Me, 1a; H, 1b; F, 1c) with the known gas electron diffraction (GED) structures, the problematic geometry of 1-methylsilatrane 1a has been revised. In particular, the new value of the Si?N distance (dSiN) in 1a turned out to be ～0.06 ? longer than the generally accepted one. This dSiN resolves the long-standing contradiction between the data of the structural and spectral experiments regarding the sensitivity of 1 to the medium effect. We also performed the ab initio and DFT study of the combined series of silatranes 1a–c, silylalkylamines H3Si(CH2)3NMe2 (2a) and F3SiCH2NMe2 (2b), silylhydrazines F3SiN(Me)NMe2 (2c) and F3SiN(SiMe3)NMe2 (2d), and silyloxyamines ClH2SiONMe2 (2e,f), (F3C)F2SiONMe2 (2g,h) and F3SiONMe2 (2i), in which the GED dSiN values are in a wide range of 2–3 ?. None of the involved quantum chemical methods has succeeded in reproducing all the experimental gas-phase dSiN values in 1a–c, 2a–i with an acceptable accuracy (0.01–0.03 ?). The problems of the used methods, primarily CCSD with the Pople basis sets, are caused by four molecules with the geminal SiNN and SiON fragments (2d,f–i) and dSiN < 2.3 ?. A reasonable hierarchy of computationally accessible theory levels for studying the physicochemical manifestation of the non-covalent intramolecular Si?N interactions can be constructed only at dSiN > 2.3 ?: MP2 < PBE0 ～ B3PW91 ～ SCS-MP2 < CCSD < CCSD(T).

Graphical abstract: The hierarchy of ab initio and DFT methods for describing an intramolecular non-covalent Si?N contact in the silicon compounds using electron diffraction geometries
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