Interaction of Ruthenium(II) with Terminal Alkynes: Benchmarking DFT Methods with Spectroscopic Data

Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F16%3A10323621" target="_blank" >RIV/00216208:11310/16:10323621 - isvavai.cz</a>
Result on the web
<a href="http://dx.doi.org/10.1021/acs.organomet.6b00021" target="_blank" >http://dx.doi.org/10.1021/acs.organomet.6b00021</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/acs.organomet.6b00021" target="_blank" >10.1021/acs.organomet.6b00021</a>

Result language
angličtina
Original language name
Interaction of Ruthenium(II) with Terminal Alkynes: Benchmarking DFT Methods with Spectroscopic Data
Original language description
Helium tagging infrared photodissociation (IRPD) spectroscopy for the characterization of organometallic complexes is presented. The IRPD spectrum of the [RuCp(PPh3)(PhCCH)](+) complex reveals that more than 80% of the detected ions correspond to a structure with pi-coordinated phenylacetylene, and the rest are complexes with the alkyne probably isomerized to its vinylidene form. The detected C=C and C H stretches of the terminal alkyne reflect the degree of activation of the triple bond. They are used to benchmark the popular DFT functionals used in theoretical studies of ruthenium catalysis. It is shown that there are only small differences between the methods. GGA methods (e.g., BP86 or PBEPBE) and (hybrid) meta GGA functionals (e.g., M06) provide slightly better descriptions of this system than hybrid DFT methods such as B3LYP. A notable exception is M06-2X, which significantly underestimates the activation of the C=C bond by the coordination to the ruthenium complex.
Czech name
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Czech description
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Type
J<sub>x</sub> - Unclassified - Peer-reviewed scientific article (Jimp, Jsc and Jost)
CEP classification
CC - Organic chemistry
OECD FORD branch
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Project
<a href="/en/project/GA14-20077S" target="_blank" >GA14-20077S: Non-heme iron catalysts: Investigation of reaction mechanisms</a><br>
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Publication year
2016
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

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