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首页> 外文期刊>Chemistry: A European journal >Reductive degradation of nido-1-CB8H12 into smaller-cage carborane systems via new monocarbaboranes [arachno-5-CB8H13](-) and closo-2-CB6H8
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Reductive degradation of nido-1-CB8H12 into smaller-cage carborane systems via new monocarbaboranes [arachno-5-CB8H13](-) and closo-2-CB6H8

机译：通过新的单碳硼烷[arachno-5-CB8H13]（-）和closo-2-CB6H8将Nido-1-CB8H12还原降解为小笼形碳硼烷系统

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摘要

Treatment of the nido-1-CB8H12 (1) carborane with NaBH, in THF at ambient temperature led to the isolation of the stable [arachno-5-CB8H13](-) (2(-)), which was isolated as Na+[5-CB8H13](-).1.5THF and PPh4+[5-CB8H13](-) in almost quantitative yield. Compound 2- underwent a boron-degradation reaction with concentrated hydrochloric acid to afford the arachno-4-CB7H13 (3) carborane in 70% yield, whereas reaction between 2- and excess phenyl acetylene in refluxing THF gave the [closo-2-CB6H7](-) (4-) in 66% yield. Protonation of the Cs(+)4(-)salt with concentrated H2SO4 or CF3COOH in CH2Cl2 afforded a new, highly volatile 2-CB6H8 (4) carborane in 95 % yield, the deprotonation of which with Et3N in CH2Cl2 leads quantitatively to Et3NH+[2-CB6H7](-)(Et(3)NH(+)4(-)). Both compounds 4- and 4 can be deboronated through treatment with concentrated hydrochloric acid in CH2Cl2 to yield the carbahexaborane nido-2-CB5H9 (5) in 60% yield. New compounds 2-, 3, and 4 were structurally characterised by the ab initio/GIAC/MP2/NMR method. The method gave superior results to those carried out using GIAO-HF when relating the calculated B-11 NMR chemical shifts to experimental data.
机译：在环境温度下于THF中用NaBH处理nido-1-CB8H12（1）碳硼烷导致稳定的[arachno-5-CB8H13]（-）（2（-））分离，其分离为Na + [ 5-CB8H13]（-）。1.5THF和PPh4 + [5-CB8H13]（-）几乎定量收率。化合物2-与浓盐酸进行硼降解反应，以70％的收率得到Arachno-4-CB7H13（3）碳硼烷，而2-与过量的苯基乙炔在回流的THF中反应得到[closo-2-CB6H7 ]（-）（4-），产率为66％。用浓H2SO4或CF3COOH在CH2Cl2中对Cs（+）4（-）盐进行质子化，可得到一种新的高挥发性2-CB6H8（4）碳硼烷，其在CH2Cl2中用Et3N进行的质子化可定量地导致Et3NH + [ 2-CB6H7]（-）（Et（3）NH（+）4（-））。可以通过在CH2Cl2中用浓盐酸处理使化合物4-和4脱硼，以60％的收率得到碳六硼烷nido-2-CB5H9（5）。通过从头开始/ GIAC / MP2 / NMR方法对新化合物2-，3和4进行结构表征。当将计算出的B-11 NMR化学位移与实验数据相关时，该方法比使用GIAO-HF进行的结果更好。

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