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Reversible electron transfer in organolanthanide chemistry.

Authors
  • Jaoul, Arnaud1
  • Tricoire, Maxime1
  • Moutet, Jules1
  • Cordier, Marie1
  • Clavaguéra, Carine2
  • Nocton, Grégory1
  • 1 LCM, CNRS, Ecole polytechnique, IP Paris, Route de Saclay, Palaiseau, France. , (France)
  • 2 Laboratoire de Chimie Physique, CNRS-Université Paris-Sud, Université Paris-Saclay, 15 avenue Jean Perrin, 91405 Orsay Cedex, France. , (France)
Type
Published Article
Journal
Chemistry squared
Publication Date
Jan 01, 2019
Volume
3
Pages
1–1
Identifiers
DOI: 10.28954/2019.csq.06.001
PMID: 31463472
Source
Medline
Keywords
Language
English
License
Unknown

Abstract

This article relates the synthesis and characterization of novel heterobimetallic complexes containing a low-valent lanthanide, a tetradentate redox non-innocent ligand, viz. the 4,5,9,10-tetraazaphenanthrene, taphen ligand and transition metal fragments of PdMe2 and PtMe2. The experimental results are supported by a theoretical study. Investigation of their reduction properties allowed the formation of isostructural original heterotrimetallic complexes containing two Cp*2Yb fragments and the (taphen)MMe2 (M = Pd and Pt) motifs. These complexes are stable in non-coordinating solvent such as toluene but decompose in coordinating solvents such as thf. Investigation of the internal electron transfer shows that the taphen ligand behaves as a two-electrons reservoir but is capable of transferring back only one electron in thf. This reversible electron(s) transfer is rare in organolanthanide chemistry and show the potential interest of these complexes in reductive chemistry. Additionally, the trinuclear complexes feature odd X-ray crystal structures in which a deviation of symmetry is observed. The latter observation was studied in depth using quantum chemistry calculations highlighting the role of non-covalent weak interactions.

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