Light Lanthanide Metallocenium Cations Exhibiting Weak Equatorial Anion Interactions

Jingjing Liu; Daniel Reta; Jake A. Cleghorn; Yu Xuan Yeoh; Fabrizio Ortu; Conrad Goodwin; Nicholas Chilton; David Mills

doi:10.1002/chem.201901167

Light Lanthanide Metallocenium Cations Exhibiting Weak Equatorial Anion Interactions

Jingjing Liu, Daniel Reta, Jake A. Cleghorn, Yu Xuan Yeoh, Fabrizio Ortu, Conrad Goodwin, Nicholas Chilton, David Mills

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

Abstract

As the dysprosocenium complex [Dy(Cp^ttt)₂][B(C₆F₅)₄] (Cp^ttt = C₅H₂tBu₃‐1,2,4, 1‐Dy) exhibits magnetic hysteresis at 60 K, similar lanthanide (Ln) complexes have been targeted in order to provide insights into this remarkable property. We recently reported homologous [Ln(Cp^ttt)₂][B(C₆F₅)₄] (1‐Ln) for all the heavier Ln from Gd‐Lu; herein, we extend this motif to the early Ln. We find, for the largest Ln^III cations, that contact ion pairs [Ln(Cp^ttt)₂{(C₆F₅‐κ¹‐F)B(C₆F₅)₃}] (1‐Ln; La‐Nd) are isolated from reactions of parent [Ln(Cp^ttt)₂(Cl)] (2‐Ln) with [H(SiEt₃)₂][B(C₆F₅)₄], where the anion binds weakly to the equatorial sites of [Ln(Cp^ttt)₂]⁺ through a single fluorine atom in the solid state. For smaller SmIII, [Sm(Cpttt)2][B(C₆F₅)₄] (1‐Sm) is isolated, which like heavier 1‐Ln does not exhibit equatorial anion interactions, but the Eu^III analogue 1‐Eu could not be synthesised due to the facile reduction of Eu^III precursors to Eu^II products. Thus with the exception of Eu and radioactive Pm this work constitutes a structurally similar family of Ln metallocenium complexes, over 50 years after the [M(Cp)₂]⁺ series was isolated for the 3d metals.

Original language	English
Pages (from-to)	7749-7758
Number of pages	10
Journal	Chemistry: A European Journal
Volume	25
Issue number	32
Early online date	17 Apr 2019
DOIs	https://doi.org/10.1002/chem.201901167
Publication status	Published - 7 Jun 2019

Keywords

cyclopentadienyl ligands
lanthanides
magnetic properties
metallocenes
sandwich complexes

Research Beacons, Institutes and Platforms

Dalton Nuclear Institute

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10.1002/chem.201901167

Cite this

@article{7f59dc84eb3c4d419bf8bf95113d3e19,

title = "Light Lanthanide Metallocenium Cations Exhibiting Weak Equatorial Anion Interactions",

abstract = "As the dysprosocenium complex [Dy(Cpttt)2][B(C6F5)4] (Cpttt = C5H2tBu3‐1,2,4, 1‐Dy) exhibits magnetic hysteresis at 60 K, similar lanthanide (Ln) complexes have been targeted in order to provide insights into this remarkable property. We recently reported homologous [Ln(Cpttt)2][B(C6F5)4] (1‐Ln) for all the heavier Ln from Gd‐Lu; herein, we extend this motif to the early Ln. We find, for the largest LnIII cations, that contact ion pairs [Ln(Cpttt)2{(C6F5‐κ1‐F)B(C6F5)3}] (1‐Ln; La‐Nd) are isolated from reactions of parent [Ln(Cpttt)2(Cl)] (2‐Ln) with [H(SiEt3)2][B(C6F5)4], where the anion binds weakly to the equatorial sites of [Ln(Cpttt)2]+ through a single fluorine atom in the solid state. For smaller SmIII, [Sm(Cpttt)2][B(C6F5)4] (1‐Sm) is isolated, which like heavier 1‐Ln does not exhibit equatorial anion interactions, but the EuIII analogue 1‐Eu could not be synthesised due to the facile reduction of EuIII precursors to EuII products. Thus with the exception of Eu and radioactive Pm this work constitutes a structurally similar family of Ln metallocenium complexes, over 50 years after the [M(Cp)2]+ series was isolated for the 3d metals.",

keywords = "cyclopentadienyl ligands, lanthanides, magnetic properties, metallocenes, sandwich complexes",

author = "Jingjing Liu and Daniel Reta and Cleghorn, {Jake A.} and Yeoh, {Yu Xuan} and Fabrizio Ortu and Conrad Goodwin and Nicholas Chilton and David Mills",

note = "Funding Information: We thank the China Scholarship Council (studentship for J.L.) the Engineering and Physical Sciences Research Council (Doctoral Prize Fellowship to C.A.P.G. and EP/P002560/1 for F.O. and D.R.), the Ramsay Memorial Fellowships Trust (fellowship to N.F.C.) and The University of Manchester. We thank the EPSRC UK National Electron Paramagnetic Resonance Service for access to the EPR facility and the SQUID magnetometer, and the University of Manchester for access to the Computational Shared Facility. Research data files supporting this publication are available from Mendeley Data at DOI: https://doi.org/ 10.17632/hgnvnjhz2v.1. Publisher Copyright: {\textcopyright} 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.",

year = "2019",

month = jun,

day = "7",

doi = "10.1002/chem.201901167",

language = "English",

volume = "25",

pages = "7749--7758",

journal = "Chemistry: A European Journal ",

issn = "0947-6539",

publisher = "John Wiley & Sons Ltd",

number = "32",

}

TY - JOUR

T1 - Light Lanthanide Metallocenium Cations Exhibiting Weak Equatorial Anion Interactions

AU - Liu, Jingjing

AU - Reta, Daniel

AU - Cleghorn, Jake A.

AU - Yeoh, Yu Xuan

AU - Ortu, Fabrizio

AU - Goodwin, Conrad

AU - Chilton, Nicholas

AU - Mills, David

N1 - Funding Information: We thank the China Scholarship Council (studentship for J.L.) the Engineering and Physical Sciences Research Council (Doctoral Prize Fellowship to C.A.P.G. and EP/P002560/1 for F.O. and D.R.), the Ramsay Memorial Fellowships Trust (fellowship to N.F.C.) and The University of Manchester. We thank the EPSRC UK National Electron Paramagnetic Resonance Service for access to the EPR facility and the SQUID magnetometer, and the University of Manchester for access to the Computational Shared Facility. Research data files supporting this publication are available from Mendeley Data at DOI: https://doi.org/ 10.17632/hgnvnjhz2v.1. Publisher Copyright: © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

PY - 2019/6/7

Y1 - 2019/6/7

N2 - As the dysprosocenium complex [Dy(Cpttt)2][B(C6F5)4] (Cpttt = C5H2tBu3‐1,2,4, 1‐Dy) exhibits magnetic hysteresis at 60 K, similar lanthanide (Ln) complexes have been targeted in order to provide insights into this remarkable property. We recently reported homologous [Ln(Cpttt)2][B(C6F5)4] (1‐Ln) for all the heavier Ln from Gd‐Lu; herein, we extend this motif to the early Ln. We find, for the largest LnIII cations, that contact ion pairs [Ln(Cpttt)2{(C6F5‐κ1‐F)B(C6F5)3}] (1‐Ln; La‐Nd) are isolated from reactions of parent [Ln(Cpttt)2(Cl)] (2‐Ln) with [H(SiEt3)2][B(C6F5)4], where the anion binds weakly to the equatorial sites of [Ln(Cpttt)2]+ through a single fluorine atom in the solid state. For smaller SmIII, [Sm(Cpttt)2][B(C6F5)4] (1‐Sm) is isolated, which like heavier 1‐Ln does not exhibit equatorial anion interactions, but the EuIII analogue 1‐Eu could not be synthesised due to the facile reduction of EuIII precursors to EuII products. Thus with the exception of Eu and radioactive Pm this work constitutes a structurally similar family of Ln metallocenium complexes, over 50 years after the [M(Cp)2]+ series was isolated for the 3d metals.

AB - As the dysprosocenium complex [Dy(Cpttt)2][B(C6F5)4] (Cpttt = C5H2tBu3‐1,2,4, 1‐Dy) exhibits magnetic hysteresis at 60 K, similar lanthanide (Ln) complexes have been targeted in order to provide insights into this remarkable property. We recently reported homologous [Ln(Cpttt)2][B(C6F5)4] (1‐Ln) for all the heavier Ln from Gd‐Lu; herein, we extend this motif to the early Ln. We find, for the largest LnIII cations, that contact ion pairs [Ln(Cpttt)2{(C6F5‐κ1‐F)B(C6F5)3}] (1‐Ln; La‐Nd) are isolated from reactions of parent [Ln(Cpttt)2(Cl)] (2‐Ln) with [H(SiEt3)2][B(C6F5)4], where the anion binds weakly to the equatorial sites of [Ln(Cpttt)2]+ through a single fluorine atom in the solid state. For smaller SmIII, [Sm(Cpttt)2][B(C6F5)4] (1‐Sm) is isolated, which like heavier 1‐Ln does not exhibit equatorial anion interactions, but the EuIII analogue 1‐Eu could not be synthesised due to the facile reduction of EuIII precursors to EuII products. Thus with the exception of Eu and radioactive Pm this work constitutes a structurally similar family of Ln metallocenium complexes, over 50 years after the [M(Cp)2]+ series was isolated for the 3d metals.

KW - cyclopentadienyl ligands

KW - lanthanides

KW - magnetic properties

KW - metallocenes

KW - sandwich complexes

UR - http://www.scopus.com/inward/record.url?scp=85065790390&partnerID=8YFLogxK

U2 - 10.1002/chem.201901167

DO - 10.1002/chem.201901167

M3 - Article

C2 - 30994214

AN - SCOPUS:85065790390

VL - 25

SP - 7749

EP - 7758

JO - Chemistry: A European Journal

JF - Chemistry: A European Journal

SN - 0947-6539

IS - 32

ER -

Light Lanthanide Metallocenium Cations Exhibiting Weak Equatorial Anion Interactions

Abstract

Keywords

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