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Effect of crystal packing on the structures of polymeric metallocenes

Författare:
Publiceringsår: 2005
Språk: Engelska
Sidor: 964-968
Publikation/Tidskrift/Serie: INORGANIC CHEMISTRY
Volym: 44
Nummer: 4
Dokumenttyp: Artikel
Förlag: American Chemical Society

Sammanfattning

The pressure dependencies of the crystal structures of the polymeric metallocenes lithium cyclopentadienide (LiCp) and potassium cyclopentadienide (KCp) have been determined by synchrotron X-ray powder diffraction. The decrease of the volume of LiCp by 34% up to a pressure of p = 12.2 GPa and of KCp by 23% at p = 5.3 GPa as well as the bulk moduli of K = 7.7 GPa for LiCp and 4.9 GPa for KCp indicate a high compressibility for these compounds. The crystal structures of KCp have been determined up to p = 3.9 GPa. An increase of the bend angle is found from 450 at P = 0 GPa up to 510 at p = 3.9 GPa. This variation is completely explained by a model invoking attractive K+ Cp- interaction and repulsive nonbonded carbon-carbon interactions. It is proposed that the bend angle in the polymeric alkali metal metallocenes is the result of the optimization of the crystal packing.

Disputation

Nyckelord

  • Chemistry

Övriga

Published
Yes
  • ISSN: 0020-1669

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