Deuteron quadrupole coupling in hydrogen bonded systems. IV. Deuteron quadrupole coupling in substituted phenols
Deuteron quadrupole coupling in hydrogen bonded systems. IV. Deuteron quadrupole coupling in substituted phenols
复制标题
氢键系统中的氘核四极耦合。
DOI：
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发表时间：
1981
期刊：
影响因子：
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通讯作者：
J. Ragle
中科院分区：
文献类型：
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作者：
L. S. Batchelder;J. Clymer;J. Ragle
用环质子的能级交叉双共振方法，观察到了氯代酚中氘原子与氧原子的纯核四极谱。所观察到的耦合常数，范围从200到250 kHz，表现出强氢键的影响，通过它们的相关性与分子间的O-H-H-O键长在那些情况下，结构数据是可用的。这在下文中解释为表明氯取代的主要作用是其通过修饰羟基旋转的屏障而对分子间氢键施加的影响。从所观察到的距离依赖性的外推，可以获得氘在非氢键键合的苯酚中的氧位置处的耦合常数为1.283 kHz。使用苯酚、乙烯醇和氯乙烯醇的模型计算对这些数据进行解释。内部旋转的障碍，以及依赖的氘四极耦合常数的取向的-OD…
The pure nuclear quadrupole spectrum of deuterium at oxygen in chlorinated phenols has been observed by level crossing double resonance with the ring protons. Observed coupling constants, ranging from 200 to 250 kHz, exhibit the effects of strong hydrogen bonding through their correlation with the intermolecular O–H⋅⋅⋅O bond lengths in those cases where structure data are available. This is interpreted below to indicate that a primary effect of chlorine substitution is the influence it exerts on intermolecular hydrogen bonding through modification of the barrier to hydroxyl group rotation. From an extrapolation of the observed distance dependence, one may obtain a coupling constant of ∼283 kHz for deuterium at the oxygen position in non‐hydrogen‐bonded phenol. An interpretation of these data is made using model calculations on phenol, vinyl alcohol, and chlorovinyl alcohol. Barriers to internal rotation, as well as the dependence of the deuterium quadrupole coupling constant on the orientation of the –OD ...