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Journal Articles Physical Chemistry Chemical Physics Year : 2022

Accurate computed singlet–triplet energy differences for cobalt systems: implication for two-state reactivity

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Abstract

Accurate singlet-triplet energy differences for cobalt and rhodium complexes were calculated by using several wave function methods, such as MRCISD, CASPT2, CCSD(T) and BCCD(T). The considered systems are built by increasing progressively the first coordination sphere around the metal. We included in our set two CpCoX complexes (Cp = cyclopentadienyl, X = alkenyl ligand), which have been suggested as intermediates in cycloaddition reactions, presenting a two-state reactivity. Most of the considered systems display a triplet ground state. However, in the case of a reaction intermediate, while a triplet ground state was predicted on the basis of Density Functional Theory results, our calculations suggest a singlet ground state. This stems from the competition between the exchange term (stabilising the triplet) and the accessibility of an intramolecular coordination (stabilising the singlet). This finding has an impact on the general mechanism of the cycloaddition reaction. Analogous rhodium systems were also studied.
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hal-03836748 , version 1 (02-11-2022)

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Léo Chaussy, Denis Hagebaum-Reignier, Stéphane Humbel, Paola Nava. Accurate computed singlet–triplet energy differences for cobalt systems: implication for two-state reactivity. Physical Chemistry Chemical Physics, 2022, 24 (36), pp.21841-21852. ⟨10.1039/D2CP03291K⟩. ⟨hal-03836748⟩
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