Choosing between Ti() and Ti(): selective reduction of titanocene dichloride by elemental lanthanides

The reduction of titanocene dichloride Cp 2 TiCl 2 with lanthanide metals has led to the discovery of a surprising lanthanide effect: while with most lanthanides, a divalent [Cp 2 Ti] equivalent was obtained, the use of samarium or ytterbium only led to the reduction to trivalent [Cp 2 TiCl]-type co...

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Bibliographic Details
Published in:Dalton transactions : an international journal of inorganic chemistry 2024-09, Vol.53 (37), p.15595-1561
Main Authors: Bousrez, Guillaume, Harakat, Dominique, Chevreux, Sylviane, Déchamps-Olivier, Isabelle, Jaroschik, Florian
Format: Article
Language:English
Subjects:
Alkynes
Chemical Sciences
Dichlorides
Lanthanides
Mass spectrometry
Samarium
Ytterbium
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Summary:The reduction of titanocene dichloride Cp 2 TiCl 2 with lanthanide metals has led to the discovery of a surprising lanthanide effect: while with most lanthanides, a divalent [Cp 2 Ti] equivalent was obtained, the use of samarium or ytterbium only led to the reduction to trivalent [Cp 2 TiCl]-type complexes, including the structurally characterized heterobimetallic complex [Cp 2 Ti(μ-Cl) 2 SmCl 2 (THF) 3 ]. These results were corroborated by reactivity studies (alkyne coupling and radical reactions), EPR spectroscopy and electrospray mass spectrometry, providing new insights into the reduction chemistry of lanthanide metals. The selective reduction of titanocene dichloride to either trivalent or divalent titanocene species depending on the lanthanide metal is described and corroborated by reactivity, ESI-MS, EPR and SCXRD studies.
ISSN:1477-9226
1477-9234
1477-9234
DOI:10.1039/d4dt02004a