Why can a gold salt react as a base?

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F17%3A10365480" target="_blank" >RIV/00216208:11310/17:10365480 - isvavai.cz</a>

Výsledek na webu

<a href="https://doi.org/10.1039/c7ob01905j" target="_blank" >https://doi.org/10.1039/c7ob01905j</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/c7ob01905j" target="_blank" >10.1039/c7ob01905j</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Why can a gold salt react as a base?

Popis výsledku v původním jazyce

This study shows that gold salts [(L) AuX] (L = PMe3, PPh3, JohnPhos, IPr; X = SbF6 , PF6, BF4, TfO, Tf2N) act as bases in aqueous solutions and can transform acetone to digold acetonyl complexes [(L)(2)Au-2(CH2COCH3)] (+) without any additional base present in solution. The key step is the formation of digold hydroxide complexes [(L)(2)Au-2(OH)] (+). The kinetics of the formation of the digold complexes and their mutual transformation is studied by electrospray ionization mass spectrometry and the delayed reactant labelling method. We show that the formation of digold hydroxide is the essential first step towards the formation of the digold acetonyl complex, the reaction is favoured by more polar solvents, and the effect of counter ions is negligible. DFT calculations suggest that digold hydroxide and digold acetonyl complexes can exist in solution only due to the stabilization by the interaction with two gold atoms. The reaction between the digold hydroxide and acetone proceeds towards the dimer {[(L) Au(OH)] u [(L) Au(CH3COCH3)] (+) }. The monomeric units interact at the gold atoms in the perpendicular arrangement typical of the gold clusters bound by the aurophilic interaction. The hydrogen is transferred

Název v anglickém jazyce

Why can a gold salt react as a base?

Popis výsledku anglicky

This study shows that gold salts [(L) AuX] (L = PMe3, PPh3, JohnPhos, IPr; X = SbF6 , PF6, BF4, TfO, Tf2N) act as bases in aqueous solutions and can transform acetone to digold acetonyl complexes [(L)(2)Au-2(CH2COCH3)] (+) without any additional base present in solution. The key step is the formation of digold hydroxide complexes [(L)(2)Au-2(OH)] (+). The kinetics of the formation of the digold complexes and their mutual transformation is studied by electrospray ionization mass spectrometry and the delayed reactant labelling method. We show that the formation of digold hydroxide is the essential first step towards the formation of the digold acetonyl complex, the reaction is favoured by more polar solvents, and the effect of counter ions is negligible. DFT calculations suggest that digold hydroxide and digold acetonyl complexes can exist in solution only due to the stabilization by the interaction with two gold atoms. The reaction between the digold hydroxide and acetone proceeds towards the dimer {[(L) Au(OH)] u [(L) Au(CH3COCH3)] (+) }. The monomeric units interact at the gold atoms in the perpendicular arrangement typical of the gold clusters bound by the aurophilic interaction. The hydrogen is transferred

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10401 - Organic chemistry

Projekt

—

Návaznosti

S - Specificky vyzkum na vysokych skolach<br>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

Organic and Biomolecular Chemistry

ISSN

1477-0520

e-ISSN

—

Svazek periodika

15

Číslo periodika v rámci svazku

37

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

12

Strana od-do

7841-7852

Kód UT WoS článku

000412825400017

EID výsledku v databázi Scopus

2-s2.0-85030258482