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

doi:10.1002/chem.201604340

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

Chemistry. 2017 Jan 26;23(6):1278-1290. doi: 10.1002/chem.201604340. Epub 2016 Dec 14.

Authors

Svetlana V Klementyeva^{1

2

3}, Nina P Gritsan^{4

5}, Marat M Khusniyarov⁶, Alexander Witt⁶, Alexey A Dmitriev^{4

5}, Elizaveta A Suturina^{5

7}, Nathan D D Hill⁸, Tracey L Roemmele⁸, Michael T Gamer², René T Boeré⁸, Peter W Roesky², Andrey V Zibarev^{4

9}, Sergey N Konchenko^{1

2

10}

Affiliations

¹ Nikolaev Institute of Inorganic Chemistry, Siberian Branch Russian Academy of Sciences, 630090, Novosibirsk, Russia.
² Institute for Inorganic Chemistry, Karlsruhe Institute of Technology (KIT), 76131, Karlsruhe, Germany.
³ Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, 603137, Nizhny Novgorod, Russia.
⁴ Department of Physics, Novosibirsk State University, 630090, Novosibirsk, Russia.
⁵ Voevodsky Institute of Chemical Kinetics and Combustion, Siberian Branch Russian Academy of Sciences, 630090, Novosibirsk, Russia.
⁶ Department of Chemistry and Pharmacy, Friedrich-Alexander-University Erlangen-Nürnberg (FAU), 91058, Erlangen, Germany.
⁷ Max Planck Institute for Chemical Energy Conversion, 45470, Mülheim an der Ruhr, Germany.
⁸ Department of Chemistry and Biochemistry, University of Lethbridge, Lethbridge, Alberta, T1K3M4, Canada.
⁹ Vorozhtsov Institute of Organic Chemistry, Siberian Branch Russian Academy of Sciences, 630090, Novosibirsk, Russia.
¹⁰ Department of Natural Sciences, Novosibirsk State University, 630090, Novosibirsk, Russia.

PMID: 27783442
DOI: 10.1002/chem.201604340

Abstract

The first lanthanide complexes with a redox-active sulfur diimide ligand, [LnCp*₂ (Me₃ SiN=)₂ S] (Ln=Sm, Eu, Yb; Cp*=η⁵ -C₅ Me₅ ), are reported. The complexes were synthesized by using [LnCp*₂ (THF)₂ ] and (Me₃ SiN=)₂ S 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 [(Me₃ SiN=)₂ S]^-^. adducts. As such, these complexes contain the first isolated and structurally characterized acyclic [(RN=)₂ S]^-^. radical anions.

Keywords: lanthanides; magnetism; quantum chemical calculations; radicals; sulfur diimide.