The First Lanthanide Complexes with a Redox-Active Sulfur Diimide Ligand

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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=SiMe₃. / Klementyeva, Svetlana V.; Gritsan, Nina P.; Khusniyarov, Marat M. et al.

In: Chemistry - A European Journal, Vol. 23, No. 6, 26.01.2017, p. 1278-1290.

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

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@article{897fcc0b68db45f5bbfe898be6e84589,

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.",

keywords = "lanthanides, magnetism, quantum chemical calculations, radicals, sulfur diimide, COORDINATION CHEMISTRY, DECAMETHYLYTTERBOCENE COMPLEXES, Z,Z CONFIGURATION, CRYSTAL-STRUCTURE, STRUCTURAL-CHARACTERIZATION, SINGLE-MOLECULE MAGNETS, TRANSITION-METAL, INTERMEDIATE-VALENCE, HETEROCYCLIC RADICAL-ANION, EXCHANGE INTERACTION",

author = "Klementyeva, {Svetlana V.} and Gritsan, {Nina P.} and Khusniyarov, {Marat M.} and Alexander Witt and Dmitriev, {Alexey A.} and Suturina, {Elizaveta A.} and Hill, {Nathan D.D.} and Roemmele, {Tracey L.} and Gamer, {Michael T.} and Boer{\'e}, {Ren{\'e} T.} and Roesky, {Peter W.} and Zibarev, {Andrey V.} and Konchenko, {Sergey N.}",

note = "{\textcopyright} 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.",

year = "2017",

month = jan,

day = "26",

doi = "10.1002/chem.201604340",

language = "English",

volume = "23",

pages = "1278--1290",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "Wiley-VCH Verlag",

number = "6",

}

RIS

TY - JOUR

T1 - The First Lanthanide Complexes with a Redox-Active Sulfur Diimide Ligand

T2 - Synthesis and Characterization of [LnCp*2(RN=)2S], Ln=Sm, Eu, Yb; R=SiMe3

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

Y1 - 2017/1/26

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.

KW - lanthanides

KW - magnetism

KW - quantum chemical calculations

KW - radicals

KW - sulfur diimide

KW - COORDINATION CHEMISTRY

KW - DECAMETHYLYTTERBOCENE COMPLEXES

KW - Z,Z CONFIGURATION

KW - CRYSTAL-STRUCTURE

KW - STRUCTURAL-CHARACTERIZATION

KW - SINGLE-MOLECULE MAGNETS

KW - TRANSITION-METAL

KW - INTERMEDIATE-VALENCE

KW - HETEROCYCLIC RADICAL-ANION

KW - EXCHANGE INTERACTION

UR - http://www.scopus.com/inward/record.url?scp=85006852922&partnerID=8YFLogxK

U2 - 10.1002/chem.201604340

DO - 10.1002/chem.201604340

M3 - Article

C2 - 27783442

AN - SCOPUS:85006852922

VL - 23

SP - 1278

EP - 1290

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

SN - 0947-6539

IS - 6

ER -

ID: 9052625

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

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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=SiMe₃