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Journal Articles ChemPhysChem Year : 2021

Triggering Electron Transfer in Co(I) Dimers: Computational Evidences for a Reversible Disproportionation Mechanism

Isabelle Fourré
Julien Pilmé
Stéphanie Halbert
Hélène Gérard

Abstract

An inner-sphere disproportionation mechanism of the Co(I) precursor CoCl(PPh3)3 is described through a Density Functional Theory study. The essential role of oleylamine in this process is unravelled. A detailed analysis of the electronic structure of Cobalt dimers of the general formula Co2Cl2Ln (L=NH3 and PH3) demonstrates that electron transfer is triggered by asymetric coordination of amine and phosphine to stabilize a mixed-valence Co(II)-Co(0) dimer. This is consistent with the HSAB statement that both amine and phosphine ligands are required to stabilize the reaction products, respectively Co(II) and Co(0) centers. We propose a quasi-athermic multi-step disproportionation mechanism with low activation barriers where the electron transfer goes through simple ligand exchanges between Co.
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Dates and versions

hal-03957603 , version 1 (26-01-2023)

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Maya Guillaumont, Isabelle Fourré, Julien Pilmé, Stéphanie Halbert, Hélène Gérard. Triggering Electron Transfer in Co(I) Dimers: Computational Evidences for a Reversible Disproportionation Mechanism. ChemPhysChem, 2021, 22 (8), pp.788-795. ⟨10.1002/cphc.202000965⟩. ⟨hal-03957603⟩
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