Stabilized Arsenic(I) Iodide: A Ready Source of Arsenic Iodide Fragments and a Useful Reagent for the Generation of Clusters

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]·2CH2Cl2. The air oxidation of [(dppe)As][I] produces crystals of the salt [Ph2P(O)CH2CH2P(OH)Ph2]2[As6I8]·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.