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Hydrogen Bonding with Hydridic Hydrogen–Experimental Low-Temperature IR and Computational Study: Is a Revised Definition of Hydrogen Bonding Appropriate?
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SYSNO ASEP 0570995 Document Type J - Journal Article R&D Document Type Journal Article Subsidiary J Článek ve WOS Title Hydrogen Bonding with Hydridic Hydrogen–Experimental Low-Temperature IR and Computational Study: Is a Revised Definition of Hydrogen Bonding Appropriate? Author(s) Civiš, Svatopluk (UFCH-W) RID, ORCID, SAI
Lamanec, M. (CZ)
Špirko, V. (CZ)
Kubišta, Jiří (UFCH-W) RID, ORCID
Špeťko, M. (CZ)
Hobza, P. (CZ)Source Title Journal of the American Chemical Society. - : American Chemical Society - ISSN 0002-7863
Roč. 145, č. 15 (2023), s. 8550-8559Number of pages 10 s. Language eng - English Country US - United States Keywords Hydrogen ; Interaction energies ; Noncovalent interactions Subject RIV CF - Physical ; Theoretical Chemistry OECD category Physical chemistry R&D Projects EF16_019/0000778 GA MŠMT - Ministry of Education, Youth and Sports (MEYS) Method of publishing Open access Institutional support UFCH-W - RVO:61388955 UT WOS 000972328900001 EID SCOPUS 85152675541 DOI https://doi.org/10.1021/jacs.3c00802 Annotation 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. Workplace J. Heyrovsky Institute of Physical Chemistry Contact Michaela Knapová, michaela.knapova@jh-inst.cas.cz, Tel.: 266 053 196 Year of Publishing 2024 Electronic address https://hdl.handle.net/11104/0342321
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