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Inorg Chem. 2004 Sep 20;43(19):5981-6.

Stabilized arsenic(i) iodide: a ready source of arsenic iodide fragments and a useful reagent for the generation of clusters.

Author information

1
Department of Chemistry and Biochemistry, University of Windsor, Windsor, Ontario, Canada N9B 3P4.

Abstract

The new stable low oxidation state arsenic(I) iodide reagent [(dppe)As][I] (dppe = 1,2-bis(diphenylphosphino)ethane) exhibits chemistry that is considerably different from its AsIII analogues. While [(dppe)As][I] is not crystalline, the crystal structure of the derivative salt [(dppe)As][(dppe)As2I7] is reported and is compared to that of [(dppe)As]2[SnCl6] x 2CH2Cl2. The air oxidation of [(dppe)As][I] produces crystals of the salt [Ph2P(O)CH2CH2P(OH)Ph2]2[As6I8] x 2CH2Cl2 and suggests that, in contrast to previous studies, the reaction of the univalent arsenic iodide salt with certain oxidants results in the oxidation of the dppe ligand and the release of "AsI-I" fragments that oligomerize to form AsI clusters. Such reactivity is confirmed by the reaction of 6[(dppe)As][I] with 12Me3NO and 2[PPh4][I] to produce [PPh4]2[As6I8] and 6dppeO2. The reactivity is rationalized using density functional theory calculations.

PMID:
15360247
DOI:
10.1021/ic049281s

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