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Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...
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Polysulfide Coordination Clusters of the Lanthanides.

Ying-Zhao Ma1, Sebastian Bestgen1, Michael T Gamer1

  • 1Institute of Inorganic Chemistry, Karlsruhe Institute of Technology, Engesserstrasse 15, 76131, Karlsruhe, Germany.

Angewandte Chemie (International Ed. in English)
|September 1, 2017
PubMed
Summary

Researchers synthesized novel trinuclear lanthanide polysulfide coordination clusters. These represent the first f-element clusters with extended polysulfide chains, formed via reductive sulfur cleavage.

Keywords:
coordination clusterslanthanidessamariumsulfurytterbium

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Area of Science:

  • Organometallic Chemistry
  • Inorganic Chemistry
  • Lanthanide Chemistry

Background:

  • Lanthanide complexes are crucial in various chemical applications.
  • Polysulfide coordination chemistry remains an underexplored area.
  • Elemental sulfur (S8) offers a rich source for polysulfide ligand synthesis.

Purpose of the Study:

  • To synthesize and characterize novel f-element polysulfide coordination clusters.
  • To investigate the formation of extended polysulfide units in lanthanide complexes.
  • To explore the reactivity of divalent lanthanides with elemental sulfur.

Main Methods:

  • Reaction of [(DippForm)2Ln(thf)2] with excess elemental sulfur in toluene.
  • Formation of trinuclear polysulfide coordination clusters [(DippForm)3Ln3S12].
  • Characterization of the resulting lanthanide-sulfur clusters.

Main Results:

  • Successful synthesis of trinuclear clusters [(DippForm)3Ln3S12] where Ln = Samarium (Sm) and Ytterbium (Yb).
  • These clusters feature the first observed f-element coordination clusters (Ln n S x ) with polysulfide units where n and x > 2.
  • The formation mechanism involves the reductive cleavage of the S8 ring by divalent lanthanides.

Conclusions:

  • Divalent lanthanides can reductively cleave elemental sulfur (S8) to form extended polysulfide chains.
  • The synthesized clusters represent a new class of f-element polysulfide coordination compounds.
  • This work expands the scope of lanthanide coordination chemistry and polysulfide cluster synthesis.