Hydrogen Bonding with Hydridic Hydrogen–Experimental Low-Temperature IR and Computational Study: Is a Revised Definition of Hydrogen Bonding Appropriate?
Identifikátory výsledku
Kód výsledku v IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F23%3A00570995" target="_blank" >RIV/61388955:_____/23:00570995 - isvavai.cz</a>
Nalezeny alternativní kódy
RIV/61388963:_____/23:00570904 RIV/61989592:15310/23:73620674 RIV/61989100:27740/23:10252378
Výsledek na webu
<a href="https://hdl.handle.net/11104/0342321" target="_blank" >https://hdl.handle.net/11104/0342321</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/jacs.3c00802" target="_blank" >10.1021/jacs.3c00802</a>
Alternativní jazyky
Jazyk výsledku
angličtina
Název v původním jazyce
Hydrogen Bonding with Hydridic Hydrogen–Experimental Low-Temperature IR and Computational Study: Is a Revised Definition of Hydrogen Bonding Appropriate?
Popis výsledku v původním jazyce
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.
Název v anglickém jazyce
Hydrogen Bonding with Hydridic Hydrogen–Experimental Low-Temperature IR and Computational Study: Is a Revised Definition of Hydrogen Bonding Appropriate?
Popis výsledku anglicky
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.
Klasifikace
Druh
J<sub>imp</sub> - Článek v periodiku v databázi Web of Science
CEP obor
—
OECD FORD obor
10403 - Physical chemistry
Návaznosti výsledku
Projekt
Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.
Návaznosti
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Ostatní
Rok uplatnění
2023
Kód důvěrnosti údajů
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Údaje specifické pro druh výsledku
Název periodika
Journal of the American Chemical Society
ISSN
0002-7863
e-ISSN
1520-5126
Svazek periodika
145
Číslo periodika v rámci svazku
15
Stát vydavatele periodika
US - Spojené státy americké
Počet stran výsledku
10
Strana od-do
8550-8559
Kód UT WoS článku
000972328900001
EID výsledku v databázi Scopus
2-s2.0-85152675541