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

Citation:

Klementyeva SV, Gritsan NP, Khusniyarov MM, Witt A, Dmitriev AA, Suturina EA, Hill NDD, Roemmele TL, Gamer MT, Boeré RT, et al. {{The First Lanthanide Complexes with a Redox-Active Sulfur Diimide Ligand: Synthesis and Characterization of [LnCp*(2)(RN=)(2)S]. CHEMISTRY-A EUROPEAN JOURNAL. 2017;23:1278-1290.

Abstract:

The first lanthanide complexes with a redox-active sulfur diimide ligand, [LnCp*(2)(Me3SiN=)(2)S] (Ln= Sm, Eu, Yb; Cp*=eta(5)-C5Me5), are reported. The complexes were synthesized by using [LnCp*(2)(THF)(2)] and (Me3SiN=)(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 in-terpreted 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=)(2)S]-(center dot) adducts. As such, these complexes contain the first isolated and structurally characterized acyclic [(RN=)(2)S](-center dot) radical anions.