Hydrogen peroxide adducts of triarylphosphine oxides

Abstract

Five new hydrogen peroxide adducts of phosphine oxides (p-Tol₃PO·H₂O₂)₂ (1), (o-Tol₃PO·H₂O₂)₂ (2), (o-Tol₂PhPO·H₂O₂)₂ (3), (p-Tol₃PO)₂·H₂O₂ (4), and (o-TolPh₂PO)₂·H₂O₂ (5), and the water adduct (o-Tol₂PhPO·H₂O)₂ (6) have been synthesized and fully characterized. Their single crystal X-ray structures have been determined and analyzed. The IR and ³¹P NMR data are in accordance with strong hydrogen bonding of the hydrogen peroxide. The mono- versus dimeric nature of the adduct assemblies has been investigated by DOSY NMR experiments. Raman spectroscopy of the symmetric adducts and the ν(O–O) stretching bands confirm the presence of hydrogen-bonded hydrogen peroxide in the solid materials. The solubilities in organic solvents have been quantified. Due to the high solubilities of 1–6 in organic solvents their ¹⁷O NMR spectra could be recorded in natural abundance, providing well-resolved signals for the PO and O–O groups. The adducts 1–5 have been probed regarding their stability in solution at 105 °C. The decomposition of the adduct 1 takes place by loss of the active oxygen atoms in two steps.