Structural, Spectroscopic, and Theoretical Comparison of Traditional vs Recently Discovered Ln2+ Ions in the [K(2.2.2-cryptand)][(C5H4SiMe3)3Ln] Complexes: The Variable Nature of Dy2+ and Nd2+

The Ln(3+) and Ln(2+) complexes, Cp'(3)Ln, 1, (Cp' = C5H4SiMe3) and [K(2.2.2-cryptand)][Cp'(3)Ln], 2, respectively, have been synthesized for the six lanthanides traditionally known in +2 oxidation states, i.e., Ln = Eu, Yb, Sm, Tm, Dy, and Nd, to allow direct structural and spectroscopic comparison with the recently discovered Ln(2)+ ions of Ln = Pr, Gd, Tb, Ho, Y, Er, and Lu in 2. 2-La and 2-Ce were also prepared to allow the first comparison of all the lanthanides in the same coordination environment in both +2 and +3 oxidation states. 2-La and 2-Ce show the same unusual structural feature of the recently discovered +2 complexes, that the Ln(Cp' ring centroid) distances are only about 0.03 angstrom longer than in the +3 analogs, 1. The Eu, Yb, Sm, Tm, Dy, and Nd complexes were expected to show much larger differences, but this was observed for only four of these traditional six lanthanides. 2-Dy and 2-Nd are like the new nine ions in this tris(cyclopentadienyl) coordination geometry. A DFT-based model explains the results and shows that a 4f(n)5d(1) electron configuration is appropriate not only for the nine recently discovered Ln(2)+ ions in 2 but also for Dy-2+ and Nd-2+, which traditionally have 4f(n)+(1) electron configurations like Eu-2+, Yb-2+, Sm-2+, and Tm-2+. These results indicate that the ground state of a lanthanide ion in a molecule can be changed by the ligand set, a previously unknown option with these metals due to the limited radial extension of the 4f orbitals.