Hydrogen Bonding with Hydridic Hydrogen–Experimental Low-Temperature IR and Computational Study: Is a Revised Definition of Hydrogen Bonding Appropriate?

0570995 - ÚFCH JH 2024 RIV US eng J - Journal Article
Civiš, Svatopluk - Lamanec, M. - Špirko, V. - Kubišta, Jiří - Špeťko, M. - Hobza, P.
Hydrogen Bonding with Hydridic Hydrogen–Experimental Low-Temperature IR and Computational Study: Is a Revised Definition of Hydrogen Bonding Appropriate?
Journal of the American Chemical Society. Roč. 145, č. 15 (2023), s. 8550-8559. ISSN 0002-7863. E-ISSN 1520-5126
R&D Projects: GA MŠMT EF16_019/0000778
Grant - others:ERDF(CZ) CZ.02.1.01/0.0/0.0/16_019/0000778
Institutional support: RVO:61388955
Keywords : Hydrogen * Interaction energies * Noncovalent interactions
OECD category: Physical chemistry
Impact factor: 15, year: 2022
Method of publishing: Open access

Spectroscopic characteristics of Me3Si–H···Y complexes (Y = ICF3, BrCN, and HCN) containing a hydridic hydrogen were determined experimentally by low-temperature IR experiments based on the direct spectral measurement of supersonically expanded intermediates on a cold substrate or by the technique of argon-matrix isolation as well as computationally at harmonic and one-dimensional anharmonic levels. The computations were based on DFT-D, MP2, MP2-F12, and CCSD(T)-F12 levels using various extended AO basis sets. The formation of all complexes related to the redshift of the Si–H stretching frequency upon complex formation was accompanied by an increase in its intensity. Similar results were obtained for another 10 electron acceptors of different types, positive σ-, π-, and p-holes and cations. The formation of HBe–H···Y complexes, studied only computationally and again containing a hydridic hydrogen, was characterized by the blueshift of the Be–H stretching frequency upon complexation accompanied by an increase in its intensity. The spectral shifts and stabilization energies obtained for all presently studied hydridic H-bonded complexes were comparable to those in protonic H-bonded complexes, which has prompted us to propose a modification of the existing IUPAC definition of H-bonding that covers, besides the classical protonic form, the non-classical hydridic and dihydrogen forms.
Permanent Link: https://hdl.handle.net/11104/0342321