Evaluating the electronic structure of formal Ln^II ions in Ln^II(C₅H₄SiMe₃)₃^1- using XANES spectroscopy and DFT calculations.

ABSTRACT: The isolation of [K(2.2.2-cryptand)][Ln(C₅H₄SiMe₃)₃], formally containing Ln^II, for all lanthanides (excluding Pm) was surprising given that +2 oxidation states are typically regarded as inaccessible for most 4f-elements. Herein, X-ray absorption near-edge spectroscopy (XANES), ground-state density functional theory (DFT), and transition dipole moment calculations are used to investigate the possibility that Ln(C₅H₄SiMe₃)₃^1- (Ln = Pr, Nd, Sm, Gd, Tb, Dy, Y, Ho, Er, Tm, Yb and Lu) compounds represented molecular Ln^II complexes. Results from the ground-state DFT calculations were supported by additional calculations that utilized complete-active-space multi-configur

SUBMITTER: Fieser ME 

PROVIDER: S-EPMC5625586 | biostudies-literature | 2017 Sep

REPOSITORIES: biostudies-literature