title: 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.
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.
authors: Nikolaev Institute of Inorganic Chemistry, Siberian Branch Russian Academy of Sciences, 630090, Novosibirsk, Russia.|Institute for Inorganic Chemistry, Karlsruhe Institute of Technology (KIT), 76131, Karlsruhe, Germany.|Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, 603137, Nizhny Novgorod, Russia.
authors: Svetlana V
authors: SV
authors: Klementyeva
authors: Department of Physics, Novosibirsk State University, 630090, Novosibirsk, Russia.|Voevodsky Institute of Chemical Kinetics and Combustion, Siberian Branch Russian Academy of Sciences, 630090, Novosibirsk, Russia.
authors: Nina P
authors: NP
authors: Gritsan
authors: Department of Chemistry and Pharmacy, Friedrich-Alexander-University Erlangen-Nürnberg (FAU), 91058, Erlangen, Germany.
authors: Marat M
authors: MM
authors: Khusniyarov
authors: Department of Chemistry and Pharmacy, Friedrich-Alexander-University Erlangen-Nürnberg (FAU), 91058, Erlangen, Germany.
authors: Alexander
authors: A
authors: Witt
authors: Department of Physics, Novosibirsk State University, 630090, Novosibirsk, Russia.|Voevodsky Institute of Chemical Kinetics and Combustion, Siberian Branch Russian Academy of Sciences, 630090, Novosibirsk, Russia.
authors: Alexey A
authors: AA
authors: Dmitriev
authors: Voevodsky Institute of Chemical Kinetics and Combustion, Siberian Branch Russian Academy of Sciences, 630090, Novosibirsk, Russia.|Max Planck Institute for Chemical Energy Conversion, 45470, Mülheim an der Ruhr, Germany.
authors: Elizaveta A
authors: EA
authors: Suturina
authors: Department of Chemistry and Biochemistry, University of Lethbridge, Lethbridge, Alberta, T1K3M4, Canada.
authors: Nathan D D
authors: ND
authors: Hill
authors: Department of Chemistry and Biochemistry, University of Lethbridge, Lethbridge, Alberta, T1K3M4, Canada.
authors: Tracey L
authors: TL
authors: Roemmele
authors: Institute for Inorganic Chemistry, Karlsruhe Institute of Technology (KIT), 76131, Karlsruhe, Germany.
authors: Michael T
authors: MT
authors: Gamer
authors: Department of Chemistry and Biochemistry, University of Lethbridge, Lethbridge, Alberta, T1K3M4, Canada.
authors: René T
authors: http://orcid.org/0000-0003-1855-360X
authors: RT
authors: Boeré
authors: Institute for Inorganic Chemistry, Karlsruhe Institute of Technology (KIT), 76131, Karlsruhe, Germany.
authors: Peter W
authors: http://orcid.org/0000-0002-0915-3893
authors: PW
authors: Roesky
authors: Department of Physics, Novosibirsk State University, 630090, Novosibirsk, Russia.|Vorozhtsov Institute of Organic Chemistry, Siberian Branch Russian Academy of Sciences, 630090, Novosibirsk, Russia.
authors: Andrey V
authors: AV
authors: Zibarev
authors: Nikolaev Institute of Inorganic Chemistry, Siberian Branch Russian Academy of Sciences, 630090, Novosibirsk, Russia.|Institute for Inorganic Chemistry, Karlsruhe Institute of Technology (KIT), 76131, Karlsruhe, Germany.|Department of Natural Sciences, Novosibirsk State University, 630090, Novosibirsk, Russia.
authors: Sergey N
authors: http://orcid.org/0000-0001-8206-2835
authors: SN
authors: Konchenko
keywords: lanthanides; magnetism; quantum chemical calculations; radicals; sulfur diimide