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The Synthesis of [Sn10(Si(SiMe3)3)4]2- Using a Metastable Sn(I) Halide Solution Synthesized via a Co-condensation Technique
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Hypervalent hydridosilicates: synthesis, structure and hydride bridging.

Paul D Prince1, Michael J Bearpark, G Sean McGrady

  • 1Department of Chemistry, King's College London, Strand, London, UKWC2R 2LS.

Dalton Transactions (Cambridge, England : 2003)
|December 22, 2007
PubMed
Summary
This summary is machine-generated.

New hydridosilicate anions were synthesized and characterized. These compounds exhibit trigonal bipyramidal structures and show potential as hydride transfer reagents, though reactivity can lead to side reactions.

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Area of Science:

  • Organometallic Chemistry
  • Inorganic Chemistry
  • Materials Science

Background:

  • Hydridosilicate anions are versatile compounds with potential applications in catalysis and synthesis.
  • Understanding their structural and electronic properties is crucial for developing new chemical transformations.
  • Previous studies have explored related silicon hydride species, but a systematic investigation of structurally defined hydridosilicate anions is lacking.

Purpose of the Study:

  • To synthesize and characterize a range of novel hydridosilicate anions.
  • To elucidate the structural features and bonding characteristics of these anions using spectroscopic, X-ray diffraction, and computational methods.
  • To evaluate the reactivity of these hydridosilicate anions as hydride transfer reagents.

Main Methods:

  • Synthesis of potassium hydridosilicate salts using potassium hydride (KH) and neutral silane precursors in the presence of [18]crown-6.
  • Characterization by Nuclear Magnetic Resonance (NMR) spectroscopy and X-ray diffraction.
  • Density Functional Theory (DFT) calculations to investigate electronic structure and interactions.

Main Results:

  • Isolation and characterization of [K([18]crown-6)]+ salts of [Ph3SiH2](-), [Ph3SiF2](-), and [(p-FC6H4)3SiHF](-)/[(p-FC6H4)3SiH2](-).
  • X-ray diffraction revealed trigonal bipyramidal (TBP) geometries for the anions, with equatorial phenyl groups and axial Si-H/Si-F bonds.
  • A [H2SiOiPr3](-) salt exhibited a distorted TBP array with axial hydride ligands and Si-H[...]K and Si-O[...]K interactions.
  • Compound 1 demonstrated facile hydride exchange and acted as a hydride transfer reagent, albeit with potential side reactions.

Conclusions:

  • The study successfully prepared and characterized novel hydridosilicate anions with defined structures.
  • The observed trigonal bipyramidal geometry is influenced by electrostatic interactions rather than solely dictating the anion's structure.
  • These hydridosilicate anions show promise as hydride transfer agents, highlighting their potential in synthetic chemistry.