Please use this identifier to cite or link to this item: doi:10.22028/D291-27492
Title: Understanding the Heteroatom Effect on the Ullmann Copper-Catalyzed Cross-Coupling of X-Arylation (X = NH, O, S) Mechanism
Author(s): Andrada, Diego M.
Soria-Castro, Silvia M.
Caminos, Daniel A.
Argüello, Juan E.
Peñéñory, Alicia B.
Language: English
Title: Catalysts
Volume: 7
Issue: 12
Publisher/Platform: MDPI
Year of Publication: 2017
Free key words: copper-catalyst
Ullmann
cross-coupling
Density Functional Theory (DFT)
DDC notations: 500 Science
540 Chemistry
Publikation type: Journal Article
Abstract: Density Functional Theory (DFT) calculations have been carried out in order to unravel the governing reaction mechanism in copper-catalyzed cross-coupling Ullmann type reactions between iodobenzene (1, PhI) and aniline (2-NH, PhNH2), phenol (2-O, PhOH) and thiophenol (2-S, PhSH) with phenanthroline (phen) as the ancillary ligand. Four different pathways for the mechanism were considered namely Oxidative Addition–Reductive Elimination (OA-RE), σ-bond Metathesis (MET), Single Electron Transfer (SET), and Halogen Atom Transfer (HAT). Our results suggest that the OA-RE route, involving CuIII intermediates, is the energetically most favorable pathway for all the systems considered. Interestingly, the rate-determining step is the oxidative addition of the phenyl iodide to the metal center regardless of the nature of the heteroatom. The computed energy barriers in OA increase in the order O < S < NH. Using the Activation Strain Model (ASM) of chemical reactivity, it was found that the strain energy associated with the bending of the copper(I) complex controls the observed reactivity.
DOI of the first publication: 10.3390/catal7120388
Link to this record: urn:nbn:de:bsz:291--ds-274921
hdl:20.500.11880/28600
http://dx.doi.org/10.22028/D291-27492
ISSN: 2073-4344
Date of registration: 17-Jan-2020
Description of the related object: Supplementary Material
Related object: https://www.mdpi.com/2073-4344/7/12/388/s1
Faculty: NT - Naturwissenschaftlich- Technische Fakultät
Department: NT - Chemie
Collections:SciDok - Der Wissenschaftsserver der Universität des Saarlandes

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