Unstable intermediates. Part XCV. Electron spin resonance spectra assigned to the radicals POCl3–, POCl2, PO2Cl2, PCl2, and PCl4 in γ-irradiated POCl3, PCl3, and PCl5

A. Begum, M. Symons
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引用次数: 7

Abstract

After exposure of phosphoryl chloride to 60Co γ-rays at 77 K, three radical species were detected. One, having a large 31P hyperfine coupling of about 1350 G is thought to be POCl3–, having two strongly coupled chlorine atoms (Aiso 66 G) and one weakly coupled chlorine atom (Aisoca. 20 G). The second species, thought to be POCl2 gave an axially symmetric spectrum at 77 K, but this became isotropic on warming the sample to 100 K, when Aiso(31P) was 759 G and Aiso(35Cl) was 18 G.The third major species, thought to be PO2Cl2, had Aiso(31P) 43 G and Aiso(35Cl) 3 G. This species was probably formed from HPO2Cl2 impurity.With similar treatment, phosphorus trichloride gave PCl2 and PCl4 radicals whilst the pentachloride gave PCl4 and an unidentified radical containing two chlorine atoms.
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不稳定的中间体。XCV一部分。γ辐照POCl3、PCl3和PCl5中自由基POCl3 -、POCl2、PO2Cl2、PCl2和PCl4的电子自旋共振谱
氯化磷暴露于60Co γ射线(77 K)后,检测到3种自由基。其中一个具有1350 G左右的31P超细耦合的被认为是POCl3 -,有两个强耦合的氯原子(aiso66 G)和一个弱耦合的氯原子(aiso20 G)。第二个被认为是POCl2的物质,在77 K时给出了轴对称的光谱,但在将样品加热到100 K时,当aiso31 (p)为759 G和aiso35 (cl)为18 G时,它变成了各向同性。有Aiso(31P) 43g和Aiso(35Cl) 3g,可能是由HPO2Cl2杂质形成的。经过类似的处理,三氯化磷得到PCl2和PCl4自由基,而五氯化磷得到PCl4和一个含有两个氯原子的未知自由基。
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