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Synthesis of heteroleptic yttrium and dysprosium 1,2,4-tris(trimethylsilyl)cyclopentadienyl complexes

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posted on 2022-06-08, 13:14 authored by Sophie C Corner, Conrad AP Goodwin, Fabrizio Ortu, Peter Evans, Hongrui Zhang, Gemma K Gransbury, George FS Whitehead, David P Mills
We report the synthesis of heteroleptic dysprosium complexes of the 1,2,4-tris(trimethylsilyl)cyclopentadienyl ligand (Cp‴={C5H2(SiMe3)3-1,2,4}), and diamagnetic yttrium analogues, by salt metathesis protocols from KCp‴ and molecular lanthanoid halide or borohydride precursors: [{Ln(Cp‴)2(μ-Cl)2K}2]∞ (1-Ln; Ln = Y, Dy), [Ln(Cp‴)2(THF)(Cl)] (2-Ln; Ln = Y, Dy), [Y(Cp‴)2(η3-C3H5)] (3-Y), [Y(Cp‴)(BH4)2(THF)] (4-Y), [Dy(Cp‴)(BH4)(μ-BH4)]4 (5-Dy) and [Ln(Cp‴)2(BH4)] (6-Ln; Ln = Y, Dy); several crystals of [Dy(Cp‴)2(BH4)(THF)] (7-Dy) formed on one occasion during the isolation of 6-Dy. Efforts to prepare the isolated lanthanoid metallocenium cations [Ln(Cp‴)2]+ for Y and Dy were not successful by the anion abstraction methods investigated herein; however, several crystals of the contact ion-pair complex [Y(Cp‴)2{(μ-Ph)2BPh2}] (8-Y) formed from the reaction of 3-Y with [NEt3H][BPh4]. On one occasion during the preparation of 3-Y we isolated several crystals of [Mg(Cp‴)(THF)(μ-Cl)]2. Complexes 1-6 and [NEt3H][BPh4] were all structurally authenticated by single crystal XRD and characterised by IR spectroscopy and elemental analysis, with magnetic susceptibility for dysprosium complexes determined by the Evans method, and yttrium analogues studied by multinuclear NMR spectroscopy; complexes 7-Dy, 8-Y, and [Mg(Cp‴)(THF)(μ-Cl)]2 were characterised by single crystal XRD only. The magnetic properties of 5-Dy were probed by SQUID magnetometry and ab initio calculations.

History

Citation

Australian Journal of Chemistry - https://doi.org/10.1071/CH21314

Author affiliation

School of Chemistry, University of Leicester

Version

  • AM (Accepted Manuscript)

Published in

Australian Journal of Chemistry

Publisher

CSIRO PUBLISHING

issn

0004-9425

eissn

1445-0038

Acceptance date

2022-02-07

Copyright date

2022

Available date

2022-06-08

Language

English