TY - JOUR
T1 - Solution chemistry of arsenic selenides
T2 - Synthesis, spectroscopy and the x-ray structures of [PPh4]2[AsnSe6], n = 2,4
AU - Ansari, Mohammad A.
AU - Ibers, James A.
AU - C.O'Neal, Samuel
AU - Pennington, William T.
AU - Kolis, Joseph W.
N1 - Funding Information:
Acknowledgements-This research was kindly supported by the National Science Foundation, Grant CHE 89-22754 (to JAI) and CHE88-02217 (to JWK).
Copyright:
Copyright 2014 Elsevier B.V., All rights reserved.
PY - 1992
Y1 - 1992
N2 - 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.
AB - 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.
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U2 - 10.1016/S0277-5387(00)83735-3
DO - 10.1016/S0277-5387(00)83735-3
M3 - Article
AN - SCOPUS:0000305066
VL - 11
SP - 1877
EP - 1881
JO - Polyhedron
JF - Polyhedron
SN - 0277-5387
IS - 15
ER -