Role of O-H⋯O/S conventional hydrogen bonds in considerable Csp2 -H blue-shift in the binary systems of acetaldehyde and thioacetaldehyde with substituted carboxylic and thiocarboxylic acids

Nguyen Truong An; Nguyen Thi Duong; Nguyen Ngoc Tri; Nguyen Tien Trung

doi:10.1039/d2ra05391h

Role of O-H⋯O/S conventional hydrogen bonds in considerable C_sp² -H blue-shift in the binary systems of acetaldehyde and thioacetaldehyde with substituted carboxylic and thiocarboxylic acids

RSC Adv. 2022 Dec 9;12(54):35309-35319. doi: 10.1039/d2ra05391h. eCollection 2022 Dec 6.

Authors

Nguyen Truong An¹, Nguyen Thi Duong¹, Nguyen Ngoc Tri^{1

2}, Nguyen Tien Trung^{1

2}

Affiliations

¹ Faculty of Natural Sciences, Quy Nhon University Quy Nhon Vietnam nguyentientrung@qnu.edu.vn.
² Laboratory of Computational Chemistry and Modelling (LCCM), Quy Nhon University Quy Nhon Vietnam.

Abstract

Stable binary complexes of RCZOH⋯CH₃CHZ (R = CH₃, H, F; Z = O, S) are due to contributions from the O-H⋯O/S and C_sp² -H⋯O/S hydrogen bonds. The strength of C_sp² /O-H⋯O is 1.5 to 2 times greater than that of the C_sp² /O-H⋯S bond. The substitution of H(C_sp² ) of HCZOH by CH₃ causes a decrease in complex stability, while the opposite trend occurs for the F atom. A very large red shift of the O-H stretching frequency in O-H⋯O/S bonds was observed. A surprising C_sp² -H blue shift up to 104.5 cm^-1 was observed for the first time. It is found that the presence of O-H⋯O/S hydrogen bonds and a decisive role of intramolecular hyperconjugation interactions in the complex cause a significant blue shift of the C_sp² -H covalent bonds. A striking role of O compared to the S atom in determining the blue shift of C_sp² -H stretching vibration and stability of binary complexes is proposed. The obtained results show that the ratio of deprotonation enthalpy and proton affinity could be considered as an index for the classification of the non-conventional hydrogen bond. SAPT2+ results show that the strength of RCSOH⋯CH₃CHS complexes is dominated by electrostatic and induction energies, while a larger contribution to the stability of remaining complexes is detected for the electrostatic component.