The First Lanthanide Complexes with a Redox-Active Sulfur Diimide Ligand: 
Synthesis and Characterization of [LnCp*2(RN=) 2S], Ln= Sm, Eu, Yb; R= SiMe 3

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

doi:10.1002/chem.201604340

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The First Lanthanide Complexes with a Redox-Active Sulfur Diimide Ligand: Synthesis and Characterization of [LnCp*₂(RN=) ₂S], Ln= Sm, Eu, Yb; R= SiMe ₃

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Suturina, Elizaveta A.
Max Planck Society;

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Citation

Klementyeva, S. V., Gritsan, N. P., Khusniyarov, M. M., Witt, A., Dmitriev, A. A., Suturina, E. A., et al. (2017). The First Lanthanide Complexes with a Redox-Active Sulfur Diimide Ligand: Synthesis and Characterization of [LnCp*₂(RN=) ₂S], Ln= Sm, Eu, Yb; R= SiMe ₃. Chemistry – A European Journal, 23(6), 1278-1290. doi:10.1002/chem.201604340.

Cite as: https://hdl.handle.net/21.11116/0000-0007-17DA-A

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.