Transmetalation Reactions Triggered by Electron Transfer between Organocopper Complexes
Lozano-Lavilla, Olmo 
(Universidad de Valladolid)
Gómez-Orellana Seguín, Pablo 
(Universitat Autònoma de Barcelona. Departament de Química)
Lledós, Agustí 
(Universitat Autònoma de Barcelona. Departament de Química)
Casares, Juan A. 
(Universidad de Valladolid)
Data: |
2021 |
Resum: |
[Cu(bipy)(CF)] reacts with most aryl iodides to form heterobiphenyls by cross-coupling, but when Rf-I is used (Rf = 3,5-dicholoro-2,4,6-trifluorophenyl), homocoupling products are also formed. Kinetic studies suggest that, for the homocoupling reaction, a mechanism based on transmetalation from [Cu(bipy)(CF)] to Cu(III) intermediates formed in the oxidative addition step is at work. Density functional theory calculations show that the interaction between these Cu(III) species and the starting Cu(I) complex involves a Cu(I)-Cu(III) electron transfer concerted with the formation of an iodine bridge between the metals and that a fast transmetalation takes place in a dimer in a triplet state between two Cu(II) units. In copper-catalyzed cross-coupling reactions, electron-transfer processes between Cu(I) and Cu(III) species are overlooked behind RDS (C−X activation). Density functional theory studies considering two molecules of the catalyst and two spin states throughout the course of the reaction have revealed the feasibility of such a process and the transmetalation between Cu(II) species, justifying in this way the formation of homocoupling products. |
Ajuts: |
Agencia Estatal de Investigación PID2019-111406GB-I00 Agencia Estatal de Investigación PID2020-116861GB-I00
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Drets: |
Aquest document està subjecte a una llicència d'ús Creative Commons. Es permet la reproducció total o parcial, la distribució, la comunicació pública de l'obra i la creació d'obres derivades, fins i tot amb finalitats comercials, sempre i quan es reconegui l'autoria de l'obra original.  |
Llengua: |
Anglès |
Document: |
Article ; recerca ; Versió publicada |
Publicat a: |
Inorganic chemistry, Vol. 60, Issue 15 (August 2021) , p. 11633-11639, ISSN 1520-510X |
DOI: 10.1021/acs.inorgchem.1c01595
PMID: 34259512
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