Ascorbic Acid/Iodine and Triphenylphosphine/Iodine as Reducing Agents for the As(V)[dbnd]O Group

Abstract

The scope of ascorbic acid/iodine and triphenylphosphine/iodine in methanol for the direct reduction of arsenic(V) compounds having the As[dbnd]O group has been investigated. Ascorbic acid/iodine reduces arsonic acids, diphenylarsinic acid (but not dimethylarsinic acid), and triphenylarsine oxide. The rates of reduction depend on the electronic effects of the ligands bound to arsenic and on the hydrogen-bonding strength of the species, when present. When the As(V) compound has an [sbnd]NH ₂ or an [sbnd]NH ₃ ⁺ group, the reduction product reacts with a ketonic form of dehydroascorbic acid, giving condensation product(s). Triphenylphosphine/iodine reduced slowly the zwitterionic o-aminophenylarsonic acid but reduced faster the hydrochloric acid salt of the same acid. It reduced dimethylarsinic acid as well because the powerful electron-withdrawing Ph ₃ P ⁺coordinated to As[dbnd]O seems to outweigh the electronic and hydrogen bonding effects.

Keywords:

• Arsinic acids
• arsonic acids
• ascorbic acid
• reductions
• triphenylarsine oxide
• triphenylphosphine