Bond-valence parameters of lanthanides

Abstract

Ln-O and Ln-N bond-valence parameters have been computed in coordination complexes for lanthanides (Ln) at oxidation states other than +3 (Ce(IV), Sm(II), Eu(II) and Yb(II)). Moreover, Ln-Cl, Ln-S and Ln-C(pi-bonded) bond-valence parameters are presented, as calculated for coordination compounds. In general, the bond-valence parameters decrease in the order Ln-O > Ln-C > Ln-N > Ln-Cl > Ln-S. It has been found that the values of bond-valence parameters decrease with increasing lanthanide atomic number for coordination compounds. As expected, the values of lanthanide-oxygen and lanthanide-nitrogen bond-valence parameters diminish with increasing lanthanide oxidation state. Several examples are given where the total valence of the lanthanide ion is apparently incorrectly assigned, as well as cases where bond-valence method calculations confirm the doubtful oxidation state assignment.