Ligand effect on the periodic properties of trivalent organolanthanide complexes: a density functional study

For the first time, density functional calculations on a series of organolanthanides of the type Cp(3)Ln, Cp(2)LnCl, Cp(2)LnCl(THF) and CpLnCl(2) (Ln = La, Ce, Eu, Gd, Yb and Lu; Cp = cyclopentadienyl, C5H5; THF = tetrahydrofuran, OC4H8), which showed a periodic trend and the influence of ligands on the molecular properties for a set of tailored lanthanide complexes. The replacement of the ligands by another alters the bond lengths and has irregular trends along the lanthanide series. The increase in the (Hirshfeld) charges on going from La to Lu indicates an increase in ionic character, which is in line with the chemical hardness and softness concept while Mulliken charges failed to describe the same. (C) 2004 Elsevier B.V. All rights reserved.