13C and 31P NMR spectra of 1‐adamantylphosphoryl derivatives
13C and 31P NMR spectra of 1‐adamantylphosphoryl derivatives
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1-金刚烷基磷酰基衍生物的13C和31P NMR谱
DOI：
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发表时间：
1985
期刊：
影响因子：
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通讯作者：
A. Hanna
中科院分区：
文献类型：
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作者：
H. Duddeck;A. Hanna
本文报道了26个桥头磷酸化金刚烷（adamantyl-P（O）XY）的~（13）C和~（31）P NMR数据。α-碳的13 C化学位移取决于X和/或Y基团的电负性，并且可以通过假设从X/Y到P的pπdπ电子反馈来解释。α-碳化学位移和相应的1 J（CP）值之间有非常好的相关性。根据磷键轨道中s和p特征的比例，提出了一种尝试性的解释。对于两种双-1，3-二卤代磷酰基金刚烷，观察到令人惊讶的大4J（PP）值。
The 13C and 31P NMR data of 26 bridgehead phosphorylated adamantanes, adamantyl‐P(O)XY, are reported. The 13C chemical shifts of the α‐carbons are dependent on the X and/or Y group electronegativities, and can be interpreted by assuming pπdπ electron back‐donation from X/Y to P. As expected, 31P chemical shifts cannot be rationalized simply in similar terms. There is an extraordinarily good correlation between α‐carbon chemical shifts and the corresponding 1J(CP) values. A tentative interpretation, based on the proportions of s and p character in phosphorus bond orbitals, is presented. Surprisingly large 4J(PP) values were observed for two bis‐1,3‐dihalophosphophoryladamantanes.