Complexation studies of iodides of trivalent uranium and lanthanides (Ce and Nd) with 2,2'-bipyridine in anhydrous pyridine solutions.
In anhydrous pyridine solution at 294 K, U(III) and Ce(III) triiodides were found to form both 1:1 (ML) and 1:2 (ML(2)) complexes with bipyridine (bipy = L) while Nd(III) triodide formed only a 1:2 complex. The 1:3 (ML(3)) complexes were identified at low temperature with a large excess of L. Conductometry measurements showed for U(III) a large increase in the conductivity when increasing the molar ratio L:U. The complex UL(2) was found to be a 1:1 electrolyte and the species UI(2)(+) was more reactive toward L in comparison with UI(3). For Ce(III) and Nd(III), MI(2)(+) and MI(3) present about the same affinity for L. The stability of the complexes is limited, and U(III) possesses a slightly higher affinity for bipy than the trivalent lanthanides. Interestingly, a preference for the formation of ML(2) complex was shown for all the studied M(III) ions. The driving force for complex formation was always the enthalpy, and, surprisingly for a bidendate ligand (bipy), no favorable entropy contribution to complex formation was observed. The X-ray crystal structures of [CeI(3)(bipy)(2)(py)](4).5py.bipy and UI(3)(bipy)(2)(py).2py were determined. The structures of the molecules MI(3)(bipy)(2)(py) are almost identical for U and Ce. The mean M(III)-N(bipy) bond distances are equal to 2.67(3) A for Ce(III) and 2.65(4) A for U(III). The slightly smaller M(III)-N(bipy) distances observed for U(III) would reflect a slightly more important covalent character of the U(III)-N(bipy) bonds, in agreement with the slightly better affinity of U(III) than Ce(III) or Nd(III) toward bipy observed in solution and with the fact that the enthalpy is the driving force for complex formation.
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Service de Chimie Moléculaire, DRECAM/DSM, CEA/Saclay, 91191 Gif-sur-Yvette, France.
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Ephritikhine
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Madic
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