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

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=)₂S], 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

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

31 Citations (SciVal)

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.

Original language	English
Pages (from-to)	1278-1290
Number of pages	13
Journal	Chemistry - A European Journal
Volume	23
Issue number	6
Early online date	26 Oct 2016
DOIs	https://doi.org/10.1002/chem.201604340
Publication status	Published - 26 Jan 2017

Keywords

lanthanides
magnetism
quantum chemical calculations
radicals
sulfur diimide

ASJC Scopus subject areas

General Chemistry

Access to Document

10.1002/chem.201604340

Cite this

Klementyeva, S. V., Gritsan, N. P., Khusniyarov, M. M., Witt, A., Dmitriev, A. A., Suturina, E. A., Hill, N. D. D., Roemmele, T. L., Gamer, M. T., Boeré, R. T., Roesky, P. W., Zibarev, A. V., & Konchenko, S. N. (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=SiMe₃. Chemistry - A European Journal, 23(6), 1278-1290. https://doi.org/10.1002/chem.201604340

Klementyeva, SV, Gritsan, NP, Khusniyarov, MM, Witt, A, Dmitriev, AA, Suturina, EA, Hill, NDD, Roemmele, TL, Gamer, MT, Boeré, RT, Roesky, PW, Zibarev, AV & Konchenko, SN 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=SiMe₃', Chemistry - A European Journal, vol. 23, no. 6, pp. 1278-1290. https://doi.org/10.1002/chem.201604340

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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.",

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AU - Klementyeva, Svetlana V.

AU - Gritsan, Nina P.

AU - Khusniyarov, Marat M.

AU - Witt, Alexander

AU - Dmitriev, Alexey A.

AU - Suturina, Elizaveta A.

AU - Hill, Nathan D.D.

AU - Roemmele, Tracey L.

AU - Gamer, Michael T.

AU - Boeré, René T.

AU - Roesky, Peter W.

AU - Zibarev, Andrey V.

AU - Konchenko, Sergey N.

PY - 2017/1/26

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N2 - 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.

AB - 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.

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