Carbon Monoxide Protonation in Condensed Phases and Bonding to Surface Superacidic Brønsted Centers Full article
Journal |
PCCP: Physical Chemistry Chemical Physics
ISSN: 1463-9076 , E-ISSN: 1463-9084 |
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Output data | Year: 2016, Volume: 18, Number: 6, Pages: 4871-4880 Pages count : 10 DOI: 10.1039/c5cp07441j | ||||||
Tags | FORMYL CATION; VIBRATIONAL FREQUENCIES; ELECTRONIC-STRUCTURE; INFRARED-SPECTRUM; OXIDE SURFACES; HCO+; BAND; ACID; SPECTROSCOPY; PROBE | ||||||
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Affiliations |
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Funding (2)
1 | The Ministry of Education and Science of the Russian Federation | |
2 | Russian Foundation for Basic Research | 16-03-00357 |
Abstract:
Using infrared (IR) spectroscopy and density functional theory (DFT) calculations, interaction of CO with the strongest known pure Brønsted carborane superacids, H(CHB11Hal11) (Hal = F, Cl), was studied. CO readily interacted at room temperature with H(CHB11F11) acid, forming a mixture of bulk salts of formyl and isoformyl cations, which were in equilibrium An-⋯H+CO COH+⋯An-. The bonding of CO to the surface Brønsted centers of the weaker acid, H(CHB11Cl11), resulted in breaking of the bridged H-bonds of the acid polymers without proton transfer (PT) to CO. The binding occurred via the C atom (blue shift ΔνCO up to +155-167 cm-1, without PT) or via O atom (red shift ΔνCO up to-110 cm-1, without PT) always simultaneously, regardless of whether H+ is transferred to CO. IR spectra of all species were interpreted by B3LYP/cc-pVQZ calculations of the simple models, which adequately mimic the ability of carborane acids to form L⋯H+CO, LH+⋯CO, COH+⋯L, and CO⋯H+L compounds (L = bases). The CO bond in all compounds was triple. Acidic strength of the Brønsted centers of commonly used acid catalysts, even so-called superacidic catalysts, is not sufficient for the formation of the compounds studied
Cite:
Stoyanov E.S.
, Malykhin S.E.
Carbon Monoxide Protonation in Condensed Phases and Bonding to Surface Superacidic Brønsted Centers
PCCP: Physical Chemistry Chemical Physics. 2016. V.18. N6. P.4871-4880. DOI: 10.1039/c5cp07441j WOS Scopus РИНЦ
Carbon Monoxide Protonation in Condensed Phases and Bonding to Surface Superacidic Brønsted Centers
PCCP: Physical Chemistry Chemical Physics. 2016. V.18. N6. P.4871-4880. DOI: 10.1039/c5cp07441j WOS Scopus РИНЦ
Files:
Full text from publisher
Dates:
Submitted: | Dec 3, 2015 |
Accepted: | Jan 14, 2016 |
Published online: | Jan 14, 2016 |
Published print: | Feb 1, 2016 |
Identifiers:
Web of science | WOS:000369509100072 |
Scopus | 2-s2.0-84957560257 |
Elibrary | 26954368 |
Chemical Abstracts | 2016:94158 |
Chemical Abstracts (print) | 164:251165 |
PMID | 26805010 |
OpenAlex | W2235502827 |