Palladium-Catalyzed C-H Activation: Mass Spectrometric Approach to Reaction Kinetics in Solution

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216275%3A25310%2F17%3A39910831" target="_blank" >RIV/00216275:25310/17:39910831 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/00216208:11310/17:10363811

Výsledek na webu

<a href="http://dx.doi.org/10.1021/acs.organomet.6b00960" target="_blank" >http://dx.doi.org/10.1021/acs.organomet.6b00960</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.organomet.6b00960" target="_blank" >10.1021/acs.organomet.6b00960</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Palladium-Catalyzed C-H Activation: Mass Spectrometric Approach to Reaction Kinetics in Solution

Popis výsledku v původním jazyce

We report a new method for determination of rate constants of processes in solution using electrospray ionization mass spectrometry (ESI-MS). The investigated reaction is C-H activation of acetanilides by palladium(II)trifluoroacetate leading to stable organopalladium complexes. The rate constants can be determined from an experiment with a couple of differently substituted acetanilides being in competition for being activated by the palladium salt. The formed organopalladium complexes can be detected by ESI-MS. The time dependence is achieved by adding one of the acetanilides to the reaction mixture with a time delay. The kinetics can be then evaluated from the evolution of the ratio of the ESI-MS signals of differently substituted complexes as a function of the time delay. The Hammett analysis of the rate constants obtained for a series of meta- and para-substituted acetanilides provides a rho value of -1.5, which is in agreement with values reported for similar C-H activations. We have also investigated the very same reaction with UV-vis spectroscopy that gave us about three times smaller rate constants but the same trend with the rho value of -1.6. The rate constants determined by ESI-MS are directly linked to the occurrence of organopalladium complexes, whereas the UV-vis data are associated with an absorption spectra change that could involve more reaction steps. DFT calculations support the interpretation of the reaction mechanism as cyclopalladation and provide the rho value in the same range. The rate-determining step corresponds to the agostic C-H transition structure.

Název v anglickém jazyce

Palladium-Catalyzed C-H Activation: Mass Spectrometric Approach to Reaction Kinetics in Solution

Popis výsledku anglicky

We report a new method for determination of rate constants of processes in solution using electrospray ionization mass spectrometry (ESI-MS). The investigated reaction is C-H activation of acetanilides by palladium(II)trifluoroacetate leading to stable organopalladium complexes. The rate constants can be determined from an experiment with a couple of differently substituted acetanilides being in competition for being activated by the palladium salt. The formed organopalladium complexes can be detected by ESI-MS. The time dependence is achieved by adding one of the acetanilides to the reaction mixture with a time delay. The kinetics can be then evaluated from the evolution of the ratio of the ESI-MS signals of differently substituted complexes as a function of the time delay. The Hammett analysis of the rate constants obtained for a series of meta- and para-substituted acetanilides provides a rho value of -1.5, which is in agreement with values reported for similar C-H activations. We have also investigated the very same reaction with UV-vis spectroscopy that gave us about three times smaller rate constants but the same trend with the rho value of -1.6. The rate constants determined by ESI-MS are directly linked to the occurrence of organopalladium complexes, whereas the UV-vis data are associated with an absorption spectra change that could involve more reaction steps. DFT calculations support the interpretation of the reaction mechanism as cyclopalladation and provide the rho value in the same range. The rate-determining step corresponds to the agostic C-H transition structure.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10401 - Organic chemistry

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

2017

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

36

Číslo periodika v rámci svazku

11

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

9

Strana od-do

2072-2080

Kód UT WoS článku

000403387300005

EID výsledku v databázi Scopus

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