Solution chemistry of arsenic selenides: Synthesis, spectroscopy and the x-ray structures of [PPh4]2[AsnSe6], n = 2,4

Mohammad A. Ansari, James A. Ibers*, Samuel C.O'Neal, William T. Pennington, Joseph W. Kolis

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

57 Scopus citations

Abstract

As4Se4 and As4Se3 do not retain their solid-state structures in solution. Dissolution of As4Se4 in en/DMF (en = ethylenediamine, DMF = dimethylformamide) causes the cleavage of an AsAs bond and the formation of the As4Se62- anion. In the presence of excess polyselenide ions the remaining AsAs bond also breaks and the As2Se62- anion is produced. Reduction of As4Se4 by potassium in DMF in the presence of PPH4Cl also produces the As4Se62- anion. [PPh4]2[As4Se6] crystallizes (- 120°C) in the orthorhombic space group Pbca with cell dimensions a = 11.272(1), b = 19.817(2), c = 43.958(9) Å, Z = 8. The As4Se62- anion resembles a basket with AsSe exocyclic bonds being the handles. [PPh4]2[As2Se6] crystallizes in the monoclinic space group P21/n with cell constants a = 10.817(2), b = 13.690(4), c = 16.298(3) Å, β = 93.96(2)°, Z = 2. The As2Se62- ion has an As2Se4 ring in a trans-chair conformation with a terminal selenium atom on each arsenic atom.

Original languageEnglish (US)
Pages (from-to)1877-1881
Number of pages5
JournalPolyhedron
Volume11
Issue number15
DOIs
StatePublished - 1992

Funding

Acknowledgements-This research was kindly supported by the National Science Foundation, Grant CHE 89-22754 (to JAI) and CHE88-02217 (to JWK).

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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