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Light Lanthanide Metallocenium Cations Exhibiting Weak Equatorial Anion Interactions.

Jingjing Liu1, Daniel Reta1, Jake A Cleghorn1

  • 1School of Chemistry, The University of Manchester, Manchester, M13 9PL, UK.

Chemistry (Weinheim an Der Bergstrasse, Germany)
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Summary
This summary is machine-generated.

Dysprosodium complexes with bulky ligands show magnetic hysteresis. This study synthesizes early lanthanide analogues, revealing insights into their magnetic properties and structural variations.

Keywords:
cyclopentadienyl ligandslanthanidesmagnetic propertiesmetallocenessandwich complexes

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Area of Science:

  • Organometallic Chemistry
  • Inorganic Chemistry
  • Materials Science

Background:

  • Dysprosodium complexes exhibiting magnetic hysteresis at 60 K have spurred interest in similar lanthanide (Ln) compounds.
  • Previous work established homologous [Ln(Cpttt )2 ][B(C6 F5 )4 ] (1-Ln) for heavier lanthanides (Gd-Lu).

Purpose of the Study:

  • To synthesize and characterize early lanthanide metallocenium complexes, extending the known series of [Ln(Cpttt )2 ][B(C6 F5 )4 ] compounds.
  • To investigate the structural and electronic properties of these early lanthanide complexes and their relationship to magnetic behavior.

Main Methods:

  • Synthesis of parent [Ln(Cpttt )2 (Cl)] (2-Ln) complexes for early lanthanides (La-Nd).
  • Reaction of 2-Ln with [H(SiEt3 )2 ][B(C6 F5 )4 ] to form the target complexes.
  • Structural characterization of isolated complexes, including X-ray crystallography.

Main Results:

  • Contact ion pairs [Ln(Cpttt )2 {(C6 F5 -κ1 -F)B(C6 F5 )3 }] (1-Ln; La-Nd) were isolated, featuring weak anion binding through a fluorine atom.
  • For smaller SmIII , the non-contact ion pair [Sm(Cpttt )2 ][B(C6 F5 )4 ] (1-Sm) was obtained.
  • The EuIII analogue (1-Eu) could not be synthesized due to facile reduction to EuII.

Conclusions:

  • A structurally similar family of early lanthanide metallocenium complexes, [Ln(Cpttt )2 ][B(C6 F5 )4 ], has been established, excluding Eu and Pm.
  • The findings provide insights into the structural diversity within lanthanide metallocenium complexes and the influence of cation size on anion interactions.