Interactions of bis(2,4,4-trimethylpentyl)dithiophosphinate with Nd(III) and Cm(III) in a homogeneous medium: a comparative study of thermodynamics and coordination modes.

Abstract

Complexation of Nd(III) and Cm(III) with purified Cyanex301 (ammonium bis(2,4,4-trimethylpentyl)dithiophosphinate, denoted as HL) was studied in 1 % v/v water/ethanol under identical conditions by spectrophotometry and microcalorimetry. For Nd(III) , three successive complexes, NdL(2+) , NdL2 (+) , and NdL3 , formed in the solution. In contrast, four complexes, CmL(2+) , CmL2 (+) , CmL3 , and CmL4 (-) formed during the titration with Cm. Fluorescence lifetime measurements provided additional insight into the complexation of Cm(III) with Cyanex301. The stepwise stability constants for the CmLj ((3-j)+) (j=1-3) complexes are about one order of magnitude higher than the corresponding NdLj ((3-j)+) complexes. The enthalpies of complexation are endothermic for both Nd(III) and Cm(III) , suggesting that the energy required for desolvation exceeds the energy gained from the cation/ligand combination. Specifically, the enthalpy of complexation for CmL(2+) is 3.5 kJ mol(-1) less endothermic than that of NdL(2+) , implying stronger covalent interaction in CmL(2+) than NdL(2+) . However, the enthalpies of complexation for CmL2 (+) and NdL2 (+) are nearly identical, and the enthalpy of complexation for CmL3 (aq) becomes more endothermic than that for NdL3 (aq). The observations suggest that, in the ethanol/water media, the overall energetics of the Cm(III) /Nd(III) complexation with Cyanex301 could depend on a number of factors, including the extent of covalency, the degree of desolvation, and the coordination modes.