Department of Chemistry, Texas A&M University, College Station, TX 77842-3012, USA.
Dalton Trans. 2019 Oct 14;48(38):14312-14325. doi: 10.1039/c9dt03070k. Epub 2019 Sep 2.
Five new hydrogen peroxide adducts of phosphine oxides (p-TolPO·HO) (1), (o-TolPO·HO) (2), (o-TolPhPO·HO) (3), (p-TolPO)·HO (4), and (o-TolPhPO)·HO (5), and the water adduct (o-TolPhPO·HO) (6) have been synthesized and fully characterized. Their single crystal X-ray structures have been determined and analyzed. The IR and P 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 O NMR spectra could be recorded in natural abundance, providing well-resolved signals for the P[double bond, length as m-dash]O 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.
已合成并充分表征了五个新的氧化膦（p-TolPO·HO）（1）、（o-TolPO·HO）（2）、（o-TolPhPO·HO）（3）、（p-TolPO）·HO（4）和（o-TolPhPO）·HO（5）的过氧化氢加合物，以及水加合物（o-TolPhPO·HO）（6）。它们的单晶 X 射线结构已被确定和分析。IR 和 P NMR 数据与过氧化氢的强氢键一致。通过 DOSY NMR 实验研究了加合物组装体的单聚体与二聚体性质。对称加合物的拉曼光谱和ν（O-O）伸缩带证实了固态材料中存在氢键合的过氧化氢。已定量测定了它们在有机溶剂中的溶解度。由于 1-6 在有机溶剂中的高溶解度，可以在自然丰度下记录其 O NMR 光谱，从而为 P[双键，长度为 m-dash]O 和 O-O 基团提供了分辨率良好的信号。研究了加合物 1-5 在 105°C 下在溶液中的稳定性。加合物 1 的分解通过两个步骤失去活性氧原子发生。
