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

Svetlana V. Klementyeva, Nina P. Gritsan, Marat M. Khusniyarov, Alexander Witt, Alexey A. Dmitriev, Elizaveta A. Suturina, Nathan D.D. Hill, Tracey L. Roemmele, Michael T. Gamer, René T. Boeré, Peter W. Roesky, Andrey V. Zibarev, Sergey N. Konchenko

Research output: Contribution to journalArticlepeer-review

13 Citations (Scopus)

Abstract

The first lanthanide complexes with a redox-active sulfur diimide ligand, [LnCp*2(Me3SiN=)2S] (Ln=Sm, Eu, Yb; Cp*=η5-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 Ln3+ and [(Me3SiN=)2S] . adducts. As such, these complexes contain the first isolated and structurally characterized acyclic [(RN=)2S] . radical anions.

Original languageEnglish
Pages (from-to)1278-1290
Number of pages13
JournalChemistry - A European Journal
Volume23
Issue number6
DOIs
Publication statusPublished - 26 Jan 2017

Keywords

  • lanthanides
  • magnetism
  • quantum chemical calculations
  • radicals
  • sulfur diimide
  • COORDINATION CHEMISTRY
  • DECAMETHYLYTTERBOCENE COMPLEXES
  • Z,Z CONFIGURATION
  • CRYSTAL-STRUCTURE
  • STRUCTURAL-CHARACTERIZATION
  • SINGLE-MOLECULE MAGNETS
  • TRANSITION-METAL
  • INTERMEDIATE-VALENCE
  • HETEROCYCLIC RADICAL-ANION
  • EXCHANGE INTERACTION

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