Unveiling the underappreciated: The bonding features of C-H⋯S-S interactions observed from rotational spectroscopy

Wenqi Lv; Yugao Xu; Tingting Yang; Liuting Wang; Jinxi Huang; Haiying Huang; Gang Feng

doi:10.1063/5.0200788

Unveiling the underappreciated: The bonding features of C-H⋯S-S interactions observed from rotational spectroscopy

J Chem Phys. 2024 Apr 7;160(13):134302. doi: 10.1063/5.0200788.

Authors

Wenqi Lv¹, Yugao Xu¹, Tingting Yang¹, Liuting Wang¹, Jinxi Huang¹, Haiying Huang¹, Gang Feng¹

Affiliation

¹ School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 401331, China.

PMID: 38557843
DOI: 10.1063/5.0200788

Abstract

The C-H⋯S-S interactions are fundamentally important to understand the stability of biomacromolecules and their binding with small molecules, but they are still underappreciated. Herein, we characterized the C-H⋯S-S interactions in model molecular complexes. The rotational spectra of the complexes of diethyl disulfide with CH2CH2 and CH2CHF were measured and analyzed. All the detected structures are mainly stabilized by a C-H⋯S-S hydrogen bond, providing stabilization energies of 2.3-7.2 kJ mol-1. Incidental C-H⋯π or C-H⋯F interactions enhance the stabilization of the complexes. London dispersion, which accounts for 54%-68% of the total attractions, is the main driving force of stabilization. The provided bonding features of C-H⋯S-S are crucial for understanding the stabilizing role of this type of interaction in diverse processes such as supramolecular recognition, protein stability, and enzyme activity.