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- Title
Synthesis of heteroleptic yttrium and dysprosium 1,2,4-tris(trimethylsilyl)cyclopentadienyl complexes.
- Authors
Corner, Sophie C.; Goodwin, Conrad A. P.; Ortu, Fabrizio; Evans, Peter; Zhang, Hongrui; Gransbury, Gemma K.; Whitehead, George F. S.; Mills, David P.
- Abstract
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. We report the synthesis and characterisation of a series of heteroleptic yttrium and dysprosium 1,2,4-tris(trimethylsilyl)cyclopentadienyl complexes containing halide, borohydride or allyl co-ligands. Attempts to abstract co-ligands and install weakly coordination anions to generate lanthanoid metallocenium cations were unsuccessful, which we attribute to side reactions with 1,2,4-tris(trimethylsilyl)cyclopentadienyl rings.
- Subjects
YTTRIUM; DYSPROSIUM; AB-initio calculations; SINGLE crystals; MAGNETIC susceptibility
- Publication
Australian Journal of Chemistry, 2022, Vol 75, Issue 8/9, p684
- ISSN
0004-9425
- Publication type
Article
- DOI
10.1071/CH21314