Antipodal shielding effects in the boron-11, carbon-13, and phosphorus-31 nuclear magnetic resonance spectra of icosahedral carborane derivatives
Antipodal shielding effects in the boron-11, carbon-13, and phosphorus-31 nuclear magnetic resonance spectra of icosahedral carborane derivatives
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二十面体碳硼烷衍生物的硼 11、碳 13 和磷 31 核磁共振谱的反足屏蔽效应
DOI：
10.1021/ic50140a006
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发表时间：
1974
影响因子：
4.6
通讯作者：
L. J. Todd
中科院分区：
文献类型：
--
作者：
A. Siedle;G. Bodner;A. R. Garber;D. C. Beer;L. J. Todd
结论 本文报道的工作表明，FeCl3 可用于在一步反应中将双功能腈连接到多面体硼烷上，而不会损失第二个功能。游离的酯和酰胺基团可以转化为α-COOH基团，并且去除苯磺酸根离子将留下醇-OH基团。值得注意的是，对 tic 和 ir 数据的彻底检查未能在反应产物中检测到任何明显量的 B12HnOH2" 或 Bi2H10 (OH) 22"。显然，在不存在强质子酸且在中等温度下，C=0键和S=0键都无法成功建立与B12Hi22~的硼-氧连接，这与酸催化加成中此类键的反应性形成鲜明对比。 2’7虽然有机衍生物的产率低得令人失望，但与引言中提到的一些方法合成的类似化合物的产率相比，它们的产率毫不逊色。由于偶联和分解的严重竞争，提高B10H102衍生物的产率将是困难的。这种竞争对于B12H122~来说是微不足道的。低收益率反映了这一点
Conclusion The work reported in this paper indicates that FeCl3 can be used for the purpose of attaching bifunctional nitriles to polyhedral boranes in a one-step reaction without the loss of the second function. A free ester and amide groups can be converted to a-COOH group and removal of the benzene-sulfonate ion will leave behind an alcoholic-OH group. It is noteworthy that a thorough examination of tic and ir data failed to detect any appreciable amount of either B12HnOH2" or Bi2H10 (OH) 22" among the reaction products. Apparently in the absence of strong protonic acids and at moderate temperatures neither the C= 0 nor the S= 0 bonds succeed in es-tablishing a boron-oxygen link to B12Hi22~, in marked con-trast with the reactivity of such bonds in acid-catalyzed additions. 2’7Though the yields of organic derivatives were disappointing-ly low, they compare favorably with the yields of similar compounds synthesized by some of the methods mentioned in the Introduction. Improving the yields of B10H102-de-rivatives will be difficult due to the serious competition from coupling and decomposition. Such competition is insignifi-cant in the case of B12H122~. Here thelow yields reflect