Carboxylate-assisted C-H activation of phenylpyridines with copper, palladium and ruthenium: a mass spectrometry and DFT study

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F15%3A10311963" target="_blank" >RIV/00216208:11310/15:10311963 - isvavai.cz</a>

Výsledek na webu

<a href="http://dx.doi.org/10.1039/c5sc01729g" target="_blank" >http://dx.doi.org/10.1039/c5sc01729g</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/c5sc01729g" target="_blank" >10.1039/c5sc01729g</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Carboxylate-assisted C-H activation of phenylpyridines with copper, palladium and ruthenium: a mass spectrometry and DFT study

Popis výsledku v původním jazyce

The C-H activation of 2-phenylpyridine, catalyzed by copper(II), palladium(II) and ruthenium(II) carboxylates, was studied in the gas phase. ESI-MS, infrared multiphoton dissociation spectroscopy and quantum chemical calculations were combined to investigate the intermediate species in the reaction. Collision induced dissociation (CID) experiments and DFT calculations allowed estimation of the energy required for this C-H activation step and the subsequent acetic acid loss. Hammett plots constructed from the CID experiments using different copper carboxylates as catalysts revealed that the use of stronger acids accelerates the C-H activation step. The reasoning can be traced from the associated transition structures that suggest a concerted mechanism and the key effect of the carbon-metal bond preformation. Carboxylates derived from stronger acids make the metal atom more electrophilic and therefore shift the reaction towards the formation of C-H activated products.

Název v anglickém jazyce

Carboxylate-assisted C-H activation of phenylpyridines with copper, palladium and ruthenium: a mass spectrometry and DFT study

Popis výsledku anglicky

The C-H activation of 2-phenylpyridine, catalyzed by copper(II), palladium(II) and ruthenium(II) carboxylates, was studied in the gas phase. ESI-MS, infrared multiphoton dissociation spectroscopy and quantum chemical calculations were combined to investigate the intermediate species in the reaction. Collision induced dissociation (CID) experiments and DFT calculations allowed estimation of the energy required for this C-H activation step and the subsequent acetic acid loss. Hammett plots constructed from the CID experiments using different copper carboxylates as catalysts revealed that the use of stronger acids accelerates the C-H activation step. The reasoning can be traced from the associated transition structures that suggest a concerted mechanism and the key effect of the carbon-metal bond preformation. Carboxylates derived from stronger acids make the metal atom more electrophilic and therefore shift the reaction towards the formation of C-H activated products.

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

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2015

Kód důvěrnosti údajů

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

Název periodika

Chemical Science

ISSN

2041-6520

e-ISSN

—

Svazek periodika

6

Číslo periodika v rámci svazku

10

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

10

Strana od-do

5544-5553

Kód UT WoS článku

000361212000023

EID výsledku v databázi Scopus

2-s2.0-84941695096