Insights into the Mechanism of Reaction of [(C5Me5)2SmII(thf)2] with CO2 and COS by DFT Studies

Ludovic Castro (1) , Stéphanie Labouille (2) , Doug K Kindra , Joseph W Ziller , François Nief (2) , Williams J Evans , Laurent Maron (1)

1 LPCNO - Laboratoire de physique et chimie des nano-objets
2 DCPH - Laboratoire Hétéroéléments et Coordination

Reaction mechanisms for the oxidative reactions of CO2 and COS with [(C5Me5)2Sm] have been investigated by means of DFT methods. The experimental formation of oxalate and dithiocarbonate complexes is explained. Their formation involve the samarium(III) bimetallic complexes [(C5Me5)2Sm‐CO2‐Sm(C5Me5)2] and [(C5Me5)2Sm‐COS‐Sm(C5Me5)2] as intermediates, respectively, ruling out radical coupling for the formation of the oxalate complex.

Domaines: Chimie de coordination

Ludovic Castro, Stéphanie Labouille, Doug K Kindra, Joseph W Ziller, François Nief, et al.. Insights into the Mechanism of Reaction of [(C5Me5)2SmII(thf)2] with CO2 and COS by DFT Studies. Chemistry - A European Journal, 2012, 18 (25), pp.78867895. ⟨10.1002/chem.201103192⟩. ⟨hal-00906056⟩