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

Kód výsledku v 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>

Výsledek na webu

<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>

Jazyk výsledku

angličtina

Název v původním jazyce

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

Popis výsledku v původním jazyce

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.

Název v anglickém jazyce

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

Popis výsledku anglicky

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.

Druh

J_x - Nezařazeno - Článek v odborném periodiku (Jimp, Jsc a Jost)

CEP obor

CC - Organická chemie

OECD FORD obor

—

Projekt

<a href="/cs/project/GA14-20077S" target="_blank" >GA14-20077S: Nehemové železné katalyzátory: výzkum reakčních mechanismů</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2016

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Organometallics

ISSN

0276-7333

e-ISSN

—

Svazek periodika

35

Číslo periodika v rámci svazku

7

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

5

Strana od-do

990-994

Kód UT WoS článku

000374077200011

EID výsledku v databázi Scopus

2-s2.0-84964465072