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The First Lanthanide Complexes with a Redox-Active Sulfur Diimide Ligand: Synthesis and Characterization of [LnCp*2
Svetlana V Klementyeva1,2,3, Nina P Gritsan4,5, Marat M Khusniyarov6
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch Russian Academy of Sciences, 630090, Novosibirsk, Russia.
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.
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