Hydrogen peroxide adducts of triarylphosphine oxides
Hydrogen peroxide adducts of triarylphosphine oxides
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DOI：
10.1039/c9dt03070k
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发表时间：
2019-10-14
影响因子：
4
通讯作者：
Blumel, Janet
中科院分区：
文献类型：
--
作者：
Arp, Fabian F.;Bhuvanesh, Nattamai;Blumel, Janet
五种新的氧化膦的过氧化氢加合物（p-Tol（3）PO中心点H2 O2）（2）（1）、（o-Tol（3）PO中心点H2 O2）（2）（2）（2）、（o-Tol（2）PhPO中心点H2 O2）（2）（3）、（p-Tol（3）PO）（2）中心点H2 O2（4）和（o-TolPh（2）PO）（2）中心点H2 O2（5）和水加合物（o-Tol（2）PhPO中心点H2O）（2）（6）的合成和表征。测定并分析了它们的单晶X射线结构。IR和P-31 NMR数据与过氧化氢的强氢键合一致。已通过DOSY NMR实验研究了加合物组装体的单聚体性质与二聚体性质。对称加合物的拉曼光谱和nu（O-O）伸缩带证实了固体材料中存在氢键键合的过氧化氢。在有机溶剂中的溶解度已被量化。由于1-6在有机溶剂中的高溶解度，它们的O-17 NMR光谱可以以天然丰度记录，为P = O和O-O基团提供了良好分辨的信号。加合物1-5已经被探测了它们在105 ° C下在溶液中的稳定性。加合物1的分解通过在两个步骤中失去活性氧原子而发生。
Five new hydrogen peroxide adducts of phosphine oxides (p-Tol(3)PO center dot H2O2)(2) (1), (o-Tol(3)PO center dot H2O2)(2) (2), (o-Tol(2)PhPO center dot H2O2)(2) (3), (p-Tol(3)PO)(2)center dot H2O2 (4), and (o-TolPh(2)PO)(2)center dot H2O2 (5), and the water adduct (o-Tol(2)PhPO center dot H2O)(2) (6) have been synthesized and fully characterized. Their single crystal X-ray structures have been determined and analyzed. The IR and P-31 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 nu(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-17 NMR spectra could be recorded in natural abundance, providing well-resolved signals for the P = O and O-O groups. The adducts 1-5 have been probed regarding their stability in solution at 105 degrees C. The decomposition of the adduct 1 takes place by loss of the active oxygen atoms in two steps.