Please use this identifier to cite or link to this item:
Title: Light Lanthanide Metallocenium Cations Exhibiting Weak Equatorial Anion Interactions.
Authors: Liu, J
Reta, D
Cleghorn, JA
Yeoh, YX
Ortu, F
Goodwin, CAP
Chilton, NF
Mills, DP
First Published: 17-Apr-2019
Publisher: Wiley
Citation: Chemistry, 2019, 25(32), pp. 7749-7758
Abstract: As the dysprosocenium complex [Dy(Cpttt )2 ][B(C6 F5 )4 ] (Cpttt =C5 H2 tBu3 -1,2,4, 1-Dy) exhibits magnetic hysteresis at 60 K, similar lanthanide (Ln) complexes have been targeted to provide insights into this remarkable property. We recently reported homologous [Ln(Cpttt )2 ][B(C6 F5 )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 {(C6 F5 -κ1 -F)B(C6 F5 )3 }] (1-Ln; La-Nd) are isolated from reactions of parent [Ln(Cpttt )2 (Cl)] (2-Ln) with [H(SiEt3 )2 ][B(C6 F5 )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(C6 F5 )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.
DOI Link: 10.1002/chem.201901167
eISSN: 1521-3765
Version: Publisher Version
Status: Peer-reviewed
Type: Journal Article
Rights: Copyright © the authors, 2019. This is an open-access article distributed under the terms of the Creative Commons Attribution-Non Commercial-No Derivatives License (, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are made.
Description: Research data files supporting this publication are available from Mendeley Data at DOI:
Appears in Collections:Published Articles, Dept. of Chemistry

Files in This Item:
File Description SizeFormat 
Liu_et_al-2019-Chemistry_-_A_European_Journal.pdfPublished (publisher PDF)1.15 MBAdobe PDFView/Open

Items in LRA are protected by copyright, with all rights reserved, unless otherwise indicated.