The First Lanthanide Complexes with a Redox-Active Sulfur Diimide Ligand: Synthesis and Characterization of [LnCp*₂(RN=)₂S], Ln=Sm, Eu, Yb; R=SiMe₃

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• 作者：Dr. Svetlana V. Klementyeva ; Prof. Dr. Nina P. Gritsan ; Dr. Marat M. Khusniyarov ; Alexander Witt ; Alexey A. Dmitriev ; Dr. Elizaveta A. Suturina ; Nathan D. D. Hill ; Dr. Tracey L. Roemmele ; Dr. Michael T. Gamer ; Prof. Dr. René ; T. Boeré ; Prof. Dr. Peter W. Roesky ; Prof. Dr. Andrey V. Zibarev and Prof. Dr. Sergey N. Konchenko
• 刊名：Chemistry - A European Journal
• 出版年：2017
• 出版时间：January 26, 2017
• 年：2017
• 卷：23
• 期：6
• 页码：1278-1290
• 全文大小：3154K
• ISSN：1521-3765

文摘

The first lanthanide complexes with a redox-active sulfur diimide ligand, [LnCp*₂(Me₃SiN=)₂S] (Ln=Sm, Eu, Yb; Cp*=ηp>5p>-C₅Me₅), are reported. The complexes were synthesized by using [LnCp*₂(THF)₂] and (Me₃SiN=)₂S and have been thoroughly characterized by single-crystal X-ray diffraction, EPR spectroscopy, UV/Vis/NIR electronic absorption spectroscopy and SQUID magnetometry. The results, as interpreted by CASSCF/SOC-RASSI calculations providing a non-perturbative treatment of spin-orbit coupling, indicate that these paramagnetic complexes are best described as Lnp>3+p> and [(Me₃SiN=)₂S]p>−p>p>.p> adducts. As such, these complexes contain the first isolated and structurally characterized acyclic [(RN=)₂S]p>−p>p>.p> radical anions.