NUCLEAR MAGNETIC RESONANCE AND SUPERCONDUCTIVITY IN THE CLATHRATE SALT [Ag$sub 7$O$sub 8$]$sup +$HF$sub 2$.
NUCLEAR MAGNETIC RESONANCE AND SUPERCONDUCTIVITY IN THE CLATHRATE SALT [Ag$sub 7$O$sub 8$]$sup +$HF$sub 2$.
复制标题
笼形盐中的核磁共振和超导性[Ag$sub 7$O$sub 8$]$sup $HF$sub 2$。
DOI：
10.1021/ja01002a600
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发表时间：
1967
影响因子：
15
通讯作者：
T. Geballe
中科院分区：
文献类型：
--
作者：
A. Gossard;D. Hindermann;M. Robin;N. A. Kuebler;T. Geballe
3的性质和反应为指定结构提供了明确的证据。至少有一个双键必须具有反式构型，因为在红外光谱中在958 cm-1处存在一个强带，在NMR光谱中观察到的J值为17 cps。二反式立体化学被NMR谱的烯烃模式的复杂性排除。单反式构型3通过加合物中的H5和H6（参见8）是反式取向的（J= 14-19 cps）的事实来证实。因此，前体5中的相应质子也是反式的，预期通过热对旋环化过程由单反式化合物3形成立体化学。另一方面，全顺式-1，2：3，4：7，8-三苯并[10]轮烯或相应的双反式化合物应具有顺式稠合加合物。3，11，16看来3中的十元环是非平面的，并不代表离域的十电子系统。与[10]轮烯本身3，4相比，3的稳定性大大增加的原因可能是在这种情况下异构化为9，10-二氢萘衍生物涉及苯环的环状离域的破坏。我们非常感谢皇家学会（伦敦）的慷慨资助，并感谢PJ Garratt和D. H.威廉姆斯的宝贵讨论。
The properties and reactions of 3 provide clear evi-dence for the assigned structure. At least one of the double bonds must havethe trans configuration, in view of thepresence of a strong band at 958 cm-1 in the infrared spectrum and the observed J value of 17 cps in the nmr spectrum. The di-trans stereochemistry is excluded by the complexity of the olefinic pattern of the nmr spectrum. The mono-trans configuration 3 is confirmed by the fact that H5 and H6 (see 8) in the adducts are(rans-oriented (J= 14-19 cps). The corre-sponding protons in the precursor 5 are therefore also trans, the stereochemistry expected to be formed from the mono-trans compound 3 by a thermal disrotatory cyclization process. 4, 11, 16 On the other hand, all-c/s-1, 2: 3, 4: 7, 8-tribenz [10] annulene or the corresponding di-/ram compound should have given c/s-fused adducts. 3, 11, 16 It appears that the ten-membered ring in 3 is non-planar and does not represent a delocalized ten--elec-tron system. A reason for the greatly increased sta-bility of 3, as compared with [10] annuleneitself, 3, 4 is presumably that the isomerization to the 9, 10-dihydronaphthalene derivative in this case involves disruption of the cyclic delocalization of a benzene ring.Acknowledgment. We are indebted to the Royal Society (London) for generous financial support andto Drs. PJ Garratt and D. H. Williams for valuable discussions.