Triphenylarsine Explained

Triphenylarsine is the chemical compound with the formula As(C6H5)3. This organoarsenic compound, often abbreviated AsPh3, is a colorless crystalline solid that is used as a ligand and a reagent in coordination chemistry and organic synthesis. The molecule is pyramidal with As-C distances of 1.942–1.956 Å and C-As-C angles of 99.6–100.5°.[1]

This compound is prepared by the reaction of arsenic trichloride with chlorobenzene using sodium as the reducing agent:[2]

AsCl3 + 3 PhCl + 6 Na → AsPh3 + 6 NaCl

Reactions

Reaction of triphenylarsine with lithium gives lithium diphenylarsenide:[3]

AsPh3 + 2 Li → LiAsPh2 + LiPh

Triphenylarsine is the precursor to tetraphenylarsonium chloride, [AsPh<sub>4</sub>]Cl, a popular precipitating agent.[2]

AsPh3 forms metal complexes with metals. Most are analogues of the corresponding triphenylphosphine derivatives. Examples include [IrCl(CO)(AsPh<sub>3</sub>)]2, [RhCl(AsPh<sub>3</sub>)<sub>3</sub>], and [Fe(CO)<sub>4</sub>(AsPh<sub>3</sub>)].[4]

Tetraphenylarsonium chloride is prepared from triphenylarsine:[5]

(C6H5)3As + Br2 → (C6H5)3AsBr2

(C6H5)3AsBr2 + H2O → (C6H5)3AsO + 2 HBr

(C6H5)3AsO + C6H5MgBr → (C6H5)4AsOMgBr

(C6H5)4AsOMgBr + 3 HCl → (C6H5)4AsCl.HCl + MgBrCl

(C6H5)4AsCl.HCl + NaOH → (C6H5)4AsCl + NaCl + H2O

Notes and References

  1. Mazhar-ul-Haque, Hasan A. Tayim, Jamil Ahmed, and William Horne "Crystal and molecular structure of triphenylarsine" Journal of Chemical Crystallography Volume 15, Number 6 / 1985.
  2. article
  3. Book: cis-2-Diphenylarsinovinyldiphenylphosphine and 2-Diphenylarsinoethyldiphenylphosphine. W. Levason . C. A. Mcauliffe . Cis -2-Diphenylarsinovinyldiphenylphosphine and 2-Diphenylarsinoethyldiphenylphosphine. Inorganic Syntheses. 16. 1976. 188–192. 10.1002/9780470132470.ch50. 978-0-470-13247-0.
  4. Book: C. A. McAuliffe. Transition Metal Complexes of Phosphorus, Arsenic, and Antimony Ligands. J. Wiley. 1973. 0-470-58117-4.
  5. 10.15227/orgsyn.030.0095. Tetraphenylarsonium Chloride Hydrochloride. Organic Syntheses. 1950. 30. 95. R. L.. Shriner. Calvin N.. Wolf.