C-H Bond Activation by a Ruthenium(II) beta-Diketonate Complex: A Mechanistic Study

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F18%3A10389378" target="_blank" >RIV/00216208:11310/18:10389378 - isvavai.cz</a>

Výsledek na webu

<a href="https://doi.org/10.1002/ejoc.201800787" target="_blank" >https://doi.org/10.1002/ejoc.201800787</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/ejoc.201800787" target="_blank" >10.1002/ejoc.201800787</a>

Jazyk výsledku

angličtina

Název v původním jazyce

C-H Bond Activation by a Ruthenium(II) beta-Diketonate Complex: A Mechanistic Study

Popis výsledku v původním jazyce

Ruthenium(II)-catalysed C-H bond activation of arenes containing a functional directing group depends on the ligand coordinated to ruthenium(II). In this study, 2-phenylpyridine C-H activation catalysed by a &quot;piano-stool&quot; ruthenium(II) complex containing a fluorinated beta-diketonate ligand was examined by ESI-MS in combination with CID experiments. [Ru(beta-diketonate)((PhPy)-Ph-CT)Cl](+) was identified as an active intermediate, and its collisional activation leads to C-H activation. CID analysis indicates proton transfer from the phenylpyridine to the chlorine anion, showing HCl elimination, while the beta-diketonate ligand is retained in the complex together with the activated phenylpyridine. Furthermore, DFT calculations were performed for the neutral analogue [Ru(beta-diketonate)(PhPy)Cl] to identify all ruthenium intermediates along the C-H activation reaction pathway. The results suggest that the most stable structure of [Ru(beta-diketonate)(PhPy)Cl] has pre-activated 2-phenylpyridine with a partly developed Ru-H bond. Further, we show that K2CO3 is not directly involved in the C-H activation step and it serves in the reaction as a base.

Název v anglickém jazyce

C-H Bond Activation by a Ruthenium(II) beta-Diketonate Complex: A Mechanistic Study

Popis výsledku anglicky

Ruthenium(II)-catalysed C-H bond activation of arenes containing a functional directing group depends on the ligand coordinated to ruthenium(II). In this study, 2-phenylpyridine C-H activation catalysed by a &quot;piano-stool&quot; ruthenium(II) complex containing a fluorinated beta-diketonate ligand was examined by ESI-MS in combination with CID experiments. [Ru(beta-diketonate)((PhPy)-Ph-CT)Cl](+) was identified as an active intermediate, and its collisional activation leads to C-H activation. CID analysis indicates proton transfer from the phenylpyridine to the chlorine anion, showing HCl elimination, while the beta-diketonate ligand is retained in the complex together with the activated phenylpyridine. Furthermore, DFT calculations were performed for the neutral analogue [Ru(beta-diketonate)(PhPy)Cl] to identify all ruthenium intermediates along the C-H activation reaction pathway. The results suggest that the most stable structure of [Ru(beta-diketonate)(PhPy)Cl] has pre-activated 2-phenylpyridine with a partly developed Ru-H bond. Further, we show that K2CO3 is not directly involved in the C-H activation step and it serves in the reaction as a base.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10401 - Organic chemistry

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2018

Kód důvěrnosti údajů

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

Název periodika

European Journal of Organic Chemistry

ISSN

1434-193X

e-ISSN

—

Svazek periodika

neuveden

Číslo periodika v rámci svazku

44

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

7

Strana od-do

6107-6113

Kód UT WoS článku

000451705700009

EID výsledku v databázi Scopus

2-s2.0-85053045572