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Eight-coordinate fluoride in a silicate double-four-ring.

Maarten G Goesten1, Roald Hoffmann2, F Matthias Bickelhaupt3,4

  • 1Inorganic Materials Chemistry, Schuit Institute of Catalysis, Eindhoven University of Technology, 5600 MB Eindhoven, The Netherlands; M.G.Goesten@TUE.NL rh34@cornell.edu.

Proceedings of the National Academy of Sciences of the United States of America
|January 19, 2017
PubMed
Summary
This summary is machine-generated.

Fluoride ions stabilize silicate cages by forming hypervalent bonds within the strained double-four-ring structure. This unique stabilization mechanism, driven by fluoride

Keywords:
chemical bondinghypervalencemain-group chemistryzeolite chemistry

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Area of Science:

  • Materials Science
  • Solid-State Chemistry
  • Computational Chemistry

Background:

  • Zeolite chemistry commonly features double-four-ring (D4R) silicate structures.
  • Anions can interact with these silicate frameworks, influencing their stability.

Purpose of the Study:

  • To investigate the interaction of fluoride anions with D4R silicate structures.
  • To understand the mechanism of stabilization and hypervalent bonding.

Main Methods:

  • Computational modeling of fluoride within D4R silicate cages.
  • Analysis of bonding interactions and structural strain.

Main Results:

  • Fluoride ions coordinate covalently to eight silicon atoms within the D4R cage.
  • Structural strain in the D4R framework is crucial for stabilizing fluoride in the center.
  • This stabilization results in an unusual case of multiple hypervalence.
  • Larger halide anions (Cl-, Br-, I-) do not provide similar stabilization due to steric hindrance.

Conclusions:

  • Fluoride's small size and ability to form hypervalent bonds enable unique stabilization of D4R silicate cages.
  • The interplay of strain and hypervalent bonding presents a novel stabilization strategy.
  • This mechanism has potential applications for designing new solid-state materials.