Universität zu Köln

Fiebig, Lukas, Held, Joseph, Schmalz, Hans-Guenther ORCID: 0000-0003-0489-1827 and Schaefer, Mathias ORCID: 0000-0002-5943-4335 (2015). Individual steps of the Mizoroki-Heck reaction and intrinsic reactivity of intermediate organopalladium complexes studied in the gas phase. Eur. J. Mass Spectrom., 21 (3). S. 623 - 634. LONDON: SAGE PUBLICATIONS LTD. ISSN 1751-6838

Full text not available from this repository.

Abstract

The mechanism of the Mizoroki-Heck reaction (MHR) was analyzed by collision-induced dissociation (CID) tandem-mass spectrometry and gas-phase ion/molecule reactions (IMRs) as well as by DFT computational analysis. The MHR was performed in the gas phase and the intrinsic reactivity of important intermediates was examined individually. Kinetics and substituent effects of cationic palladiumPCy(3)-aryl complexes (Cy = cyclohexyl) with 2,3-dimethylbutadiene in the MHR were analyzed via IMRs and CID. The kinetics and ion structures of the species involved in the olefin insertion, i.e., the carbopalladation, were investigated. Moreover, linear free-energy correlations-were applied and a concerted mechanism proceeding via a four-membered transition state for the carbopalladation step that exhibited only a minor charge separation was deduced.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Fiebig, Lukas UNSPECIFIED UNSPECIFIED UNSPECIFIED Held, Joseph UNSPECIFIED UNSPECIFIED UNSPECIFIED Schmalz, Hans-Guenther UNSPECIFIED orcid.org/0000-0003-0489-1827 UNSPECIFIED Schaefer, Mathias UNSPECIFIED orcid.org/0000-0002-5943-4335 UNSPECIFIED
URN:	urn:nbn:de:hbz:38-418769
DOI:	10.1255/ejms.1310
Journal or Publication Title:	Eur. J. Mass Spectrom.
Volume:	21
Number:	3
Page Range:	S. 623 - 634
Date:	2015
Publisher:	SAGE PUBLICATIONS LTD
Place of Publication:	LONDON
ISSN:	1751-6838
Language:	English
Faculty:	Faculty of Mathematics and Natural Sciences
Divisions:	Faculty of Mathematics and Natural Sciences > Department of Chemistry > Institute of Organic Chemistry
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language PALLADIUM-CATALYZED ARYLATION; ION-MOLECULE REACTIONS; MASS-SPECTROMETRY; ELECTROSPRAY-IONIZATION; TRAP; MECHANISM; METAL; LIGAND; ARYL; DISSOCIATION Multiple languages Physics, Atomic, Molecular & Chemical; Spectroscopy Multiple languages
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/41876