Hydrogen Peroxide and Di(hydroperoxy)propane Adducts of Phosphine Oxides as Stoichiometric and Soluble Oxidizing Agents

Abstract Aqueous hydrogen peroxide is widely used as an oxidizing agent in industry and academia. Herein, the hydrogen peroxide adducts of phosphine oxides, [ t Bu 3 PO ⋅ H 2 O 2 ] 2 and [Ph 3 PO ⋅ H 2 O 2 ] 2 ⋅ H 2 O 2 , are described. Additionally, the corresponding di(hydroperoxy)propane adducts R 3 PO ⋅ (HOO) 2 CMe 2 (R=Cy, Ph) were synthesized and characterized. All adducts could be obtained as large single crystals suitable for structural characterization by X‐ray crystallography and solid‐state NMR spectroscopy. The di(hydroperoxy)propane adducts are soluble in organic solvents which enables oxidation reactions in one phase. As the adducts are solid and molecular, they can easily be applied stoichiometrically. No loss of oxidizing power occurs upon long‐term storage of the single crystals at room temperature or the powders at −20 °C.