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.

Item Type:

Journal Article (Original Article)

Division/Institute:

08 Faculty of Science > Department of Chemistry, Biochemistry and Pharmaceutical Sciences (DCBP)

UniBE Contributor:

Kleemiss, Florian and Grabowsky, Simon

Subjects:

500 Science > 570 Life sciences; biology
500 Science > 540 Chemistry

ISSN:

1089-5639

Publisher:

American Chemical Society

Language:

English

Submitter:

Simon Grabowsky

Date Deposited:

03 Jun 2021 17:01

Last Modified:

03 Jun 2021 17:01

Publisher DOI:

10.1021/acs.jpca.1c00601

BORIS DOI:

10.48350/156626

URI:

https://boris.unibe.ch/id/eprint/156626

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