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 Ln³⁺ and Ln²⁺ complexes, Cp′₃Ln, <b>1</b>, (Cp′ = C₅H₄SiMe₃) and [K­(2.2.2-cryptand)]­[Cp′₃Ln], <b>2</b>, 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 Ln²⁺ ions of Ln = Pr, Gd, Tb, Ho, Y, Er, and Lu in <b>2</b>. <b>2-La</b> and <b>2-Ce</b> were also prepared to allow the first comparison of all the lanthanides in the same coordination environment in both +2 and +3 oxidation states. <b>2-La</b> and <b>2-Ce</b> show the same unusual structural feature of the recently discovered +2 complexes, that the Ln–(Cp′ ring centroid) distances are only about 0.03 Å longer than in the +3 analogs, <b>1</b>. The Eu, Yb, Sm, Tm, Dy, and Nd complexes were expected to show much larger differences, but this was observed for <i>only four of these traditional six</i> lanthanides. <b>2-Dy</b> and <b>2-Nd</b> are like the new nine ions in this tris­(cyclopentadienyl) coordination geometry. A DFT-based model explains the results and shows that a 4f ^<i>n</i>5d¹ electron configuration is appropriate not only for the nine recently discovered Ln²⁺ ions in <b>2</b> but also for Dy²⁺ and Nd²⁺, which traditionally have 4f ^<i>n</i>+1 electron configurations like Eu²⁺, Yb²⁺, Sm²⁺, and Tm²⁺. 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