2003/01/01 by Aurélien R. Willauer, Chad T. Palumbo, Rosario Scopelliti +5 · 1 citation
Chemistry · Energy · Engineering · Materials Science · #Environmental and Ecological Studies #Lanthanide and Transition Metal Complexes #Organometallic Complex Synthesis and Catalysis #Radioactive element chemistry and processing #Smart Grid Energy Management
paper · pdf · doi:10.1002/anie.201914733
openalex publication_date 2003/01/01 · openalex created_date 2016/06/24 · openalex updated_date 2026/08/01
The synthesis of lanthanides other than cerium in the oxidation state +IV has remained a desirable but unmet target until recently, when two examples of Tb<sup>IV</sup> with saturated coordination spheres were isolated. Here we report the third example of an isolated molecular complex of terbium(IV), where the supporting siloxide ligands do not saturate the coordination sphere. The fully characterized six-coordinate complex [Tb<sup>IV</sup> (OSiPh<sub>3</sub> )<sub>4</sub> (MeCN)<sub>2</sub> ], 2-Tb<sup>Ph</sup> , shows high stability and the labile MeCN ligands can be replaced by phosphinoxide ligands. Computational studies suggest that the stability is due to a strong π(O-Tb) interaction which is stronger than in the previously reported Tb<sup>IV</sup> complexes. Cyclic-voltammetry experiments demonstrate that non-binding counterions contribute to the stability of Tb<sup>IV</sup> in solution by destabilizing the +III oxidation state, while alkali ions promote Tb<sup>IV</sup> /Tb<sup>III</sup> electron transfer.