期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 59, 期 9, 页码 3549-3553出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201914733
关键词
lanthanides; metal-ion-coupled electron transfer; rare earths; siloxides; terbium
资金
- EPFL
- Swiss National Science Foundation [200021 178793, 169699]
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-IV 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-IV(OSiPh3)(4)(MeCN)(2)], 2-Tb-Ph, 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 pi(O-Tb) interaction which is stronger than in the previously reported Tb-IV complexes. Cyclic-voltammetry experiments demonstrate that non-binding counterions contribute to the stability of Tb-IV in solution by destabilizing the +III oxidation state, while alkali ions promote Tb-IV/Tb-III electron transfer.
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