On the Role of Hydrogen Bonding in Gas-Phase S N 2 Reactions at Silicon

Fugel, Malte; Dittmer, Anneke; Kleemiss, Florian; Grabowsky, Simon (2021). On the Role of Hydrogen Bonding in Gas-Phase S N 2 Reactions at Silicon. Journal of physical chemistry. A, 125(19), pp. 4070-4078. American Chemical Society 10.1021/acs.jpca.1c00601

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The shape of the potential energy surface (PES) of gas-phase SN2reactions at silicon is determined by the type of nucleophile, the leaving group, andsubstituents which remain bonded to silicon. In this study, we present PES scans alongthe reaction coordinate of six symmetrical SN2 reactions: X−+ SiR3X→XSiR3+X−,where X = Cl or F and R = H, Me, or OMe. While thefluorine systems and theClSiH3Cl system only give single-well PESs, ClSiMe3Cl and ClSi(OMe)3Cl give triple-and double-well PESs with stable pre- and post-reaction complexes. A complementarybonding analysis (energy decomposition analysis, quantum theory of atoms in molecules, and natural bond orbitals) reveals that theleaving group (X−) is stabilized by hydrogen bonding in the XSiMe3X and XSi(OMe)3X systems. It is shown that this so farneglected stabilizing contribution, along withσ-hole bonding, is responsible for the shapes of the PESs of ClSiMe3Cl andClSi(OMe)3Cl in the gas phase.

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