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

doi:10.1016/S0277-5387(00)83735-3

Solution chemistry of arsenic selenides: Synthesis, spectroscopy and the x-ray structures of [PPh₄]₂[As_nSe₆], n = 2,4

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

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-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 As₄Se₆^2- anion. In the presence of excess polyselenide ions the remaining AsAs bond also breaks and the As₂Se₆^2- anion is produced. Reduction of As₄Se₄ by potassium in DMF in the presence of PPH₄Cl also produces the As₄Se₆^2- 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 As₄Se₆^2- 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 As₂Se₆^2- ion has an As₂Se₄ ring in a trans-chair conformation with a terminal selenium atom on each arsenic atom.

Original language	English (US)
Pages (from-to)	1877-1881
Number of pages	5
Journal	Polyhedron
Volume	11
Issue number	15
DOIs	https://doi.org/10.1016/S0277-5387(00)83735-3
State	Published - 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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10.1016/S0277-5387(00)83735-3

Cite this

@article{1b4b7d4b5ee54c59aadbbf5526556b76,

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

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) {\AA}, 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) {\AA}, 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.",

author = "Ansari, {Mohammad A.} and Ibers, {James A.} and Samuel C.O'Neal and Pennington, {William T.} and Kolis, {Joseph W.}",

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

year = "1992",

doi = "10.1016/S0277-5387(00)83735-3",

language = "English (US)",

volume = "11",

pages = "1877--1881",

journal = "Polyhedron",

issn = "0277-5387",

publisher = "Elsevier Ltd",

number = "15",

}

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).

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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