Detection of Intermediates in Dual Gold Catalysis Using High-Resolution Ion Mobility Mass Spectrometry

Benzene; Benzene refining; Catalysis; Catalysts; Chemical activation; Electrospray ionization; Gold; Ion mobility spectrometers; Mass spectrometry; Model structures; Reaction intermediates; Collision cross sections; Cooperative interactions; Density functional computations; Direct observations; High resolution; Ion mobility-mass spectrometry; Reaction mixture; Structural isomers; Isomers

Abstract :

[en] We have probed for reaction intermediates involved in the dual-gold-catalyzed activation of a conjugated 1,5-diyne substrate and its further coupling to benzene in the liquid phase. This was done by sampling the reaction mixture by electrospray ionization followed by high-resolution ion mobility mass spectrometry - under conditions allowing for the resolution of structural isomers differing in their collision cross sections by less than 0.5%. For the cationic mass corresponding to catalyst + diyne (activation stage) we resolve four isomers. At the mass corresponding to catalyst + diyne + benzene, two isomers are observed. By comparing the experimentally obtained cross sections to those inferred for model structures derived from density functional computations, we find our measurements to be consistent with the proposed solution mechanism. This constitutes the first direct observation of intermediates in dual gold catalysis and supports the previous inference that the mechanism involves cooperative interactions between two gold centers. © 2018 American Chemical Society.

Disciplines :

Chemistry

Author, co-author :

Greisch, J.-F.; Institute of Physical Chemistry, KIT, Karlsruhe, Germany, Institute of Nanotechnology, KIT, Eggenstein-Leopoldshafen, Germany

Weis, P.; Institute of Physical Chemistry, KIT, Karlsruhe, Germany

Brendle, K.; Institute of Physical Chemistry, KIT, Karlsruhe, Germany

Kappes, M. M.; Institute of Physical Chemistry, KIT, Karlsruhe, Germany, Institute of Nanotechnology, KIT, Eggenstein-Leopoldshafen, Germany

Haler, Jean ; Université de Liège - ULiège > Département de chimie (sciences) > Laboratoire de spectrométrie de masse (L.S.M.)

Far, Johann ; Université de Liège - ULiège > Département de chimie (sciences) > Center for Analytical Research and Technology (CART)

De Pauw, Edwin ; Université de Liège - ULiège > Département de chimie (sciences) > Laboratoire de spectrométrie de masse (L.S.M.)

Albers, C.; Bruker Daltonic GmbH, Bremen, Germany

Bay, S.; Organic Chemistry Institute, Heidelberg University, Heidelberg, Germany

Wurm, T.; Organic Chemistry Institute, Heidelberg University, Heidelberg, Germany

More authors (3 more)

Language :

English

Title :

Detection of Intermediates in Dual Gold Catalysis Using High-Resolution Ion Mobility Mass Spectrometry

Publication date :

2018

Journal title :

Organometallics

ISSN :

0276-7333

eISSN :

1520-6041

Publisher :

American Chemical Society

Volume :

Issue :

Pages :

1493-1500

Peer reviewed :

Peer Reviewed verified by ORBi

Funders :

Hector Fellow Academy
Hector Stiftung II
DFG - Deutsche Forschungsgemeinschaft
F.R.S.-FNRS - Fonds de la Recherche Scientifique

Available on ORBi :

since 13 June 2018

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