Department of Chemistry, Texas A&M University, P.O. Box 30012, College Station, TX 77842-3012, USA.
Dalton Trans. 2012 Feb 14;41(6):1742-54. doi: 10.1039/c1dt11863c. Epub 2011 Dec 9.
Reactions of the tertiary phosphines R(3)P (R = Me, Bu, Oct, Cy, Ph) with 35% aqueous H(2)O(2) gives the corresponding oxides as the H(2)O(2) adducts R(3)P=O·(H(2)O(2))(x) (x = 0.5-1.0). Air oxidation leads to a mixture of products due to the insertion of oxygen into one or more P-C bonds. (31)P NMR spectroscopy in solution and in the solid state, as well as IR spectroscopy reveal distinct features of the phosphine oxides as compared to their H(2)O(2) adducts. The single crystal X-ray analyses of Bu(3)P=O and Cy(3)P=O·(H(2)O(2)) show a P=O stacking motif for the phosphine oxide and a cyclic structure, in which the six oxygen atoms exhibit a chair conformation for the dimeric H(2)O(2) adduct. Different methods for the decomposition of the bound H(2)O(2) and the removal of the ensuing strongly adsorbed H(2)O are evaluated. Treating R(3)P=O·(H(2)O(2))(x) with molecular sieves destroys the bound H(2)O(2) safely under mild conditions (room temperature, toluene) within one hour and quantitatively removes the adsorbed H(2)O from the hygroscopic phosphine oxides within four hours. At 60 °C the entire decomposition/drying process is complete within one hour.
叔膦 R(3)P（R = Me、Bu、Oct、Cy、Ph）与 35%水过氧化氢反应得到相应的氧化物作为过氧化氢加合物 R(3)P=O·(H(2)O(2))(x) (x = 0.5-1.0)。由于氧插入到一个或多个 P-C 键中，空气氧化导致产物混合物。溶液和固态中的 (31)P NMR 光谱以及红外光谱表明，与过氧化氢加合物相比，膦氧化物具有明显的特征。Bu(3)P=O 和 Cy(3)P=O·(H(2)O(2))的单晶 X 射线分析表明，对于膦氧化物，P=O 堆积基序为磷氧化物，而环状结构中，六个氧原子呈现出二聚过氧化氢加合物的椅式构象。评估了不同的方法来分解结合的 H(2)O(2)并去除随之而来的强吸附的 H(2)O。用分子筛处理 R(3)P=O·(H(2)O(2))(x)可在温和条件（室温、甲苯）下在一小时内安全地破坏结合的 H(2)O(2)，并在四小时内定量去除吸湿膦氧化物中吸附的 H(2)O。在 60°C 下，整个分解/干燥过程在一小时内完成。
