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|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.
|Year of Publication:||2017|
|Free key words:||copper-catalyst|
Density Functional Theory (DFT)
|DDC notations:||500 Science |
|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|
|Date of registration:||17-Jan-2020|
|Description of the related object:||Supplementary Material|
|Faculty:||NT - Naturwissenschaftlich- Technische Fakultät|
|Department:||NT - Chemie|
|Collections:||SciDok - Der Wissenschaftsserver der Universität des Saarlandes|
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