Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 140, Issue 43, Pages 14433-14439Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.8b09081
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Funding
- French National Agency [ANR-15-CE29-0019]
- GENCI [CINES/IDRIS] [A0040806830]
- DGA
- CNRS
- Ecole polytechnique
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The Article presents the synthesis, structure, and bonding of a series of neutral and linear sandwich compounds with the cyclononatetraenyl (Cnt) ligand and divalent lanthanides. These compounds account for the emergence of the lanthanidocene series in reference to the ferrocene and uranocene. The synthetic strategy uses the solubility difference between two conformational isomers of the ligand, as well as the isomerization of the compounds induced by solvent coordination, yielding the isomorphous and isostructural neutral and rigorously linear sandwich complexes. The molecular structures feature a Cnt-Ln-Cnt angle of 180 degrees and a ring size close to the Cnt-Cnt(centroid) distance. A qualitative molecular orbital diagram is provided, in D-9d symmetry, and DFT calculations enforce the bonding model.
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