| 碳硼烷硼端衍生物的合成与表征 |
| Synthesis and Characterization of Boron-substituted o-Carborane Derivatives Containing B-C, B-Cl or B-P Bond via B-H Activation |
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| 摘要: 在路易斯酸催化下，碳硼烷分别与对氰基溴化苄、三苯基膦在甲苯溶液里回流，前者反应中，制备得碳硼烷的硼端与对氰基苄基中的亚甲基直接偶联的产物1，通过调整催化剂的含量，可以显著地提高含B-Cl键的产物2的产率；与三苯基膦的反应中，碳硼烷失去一个硼顶，并与三苯基膦中的P原子直接偶联，生成含B-P键的巢式碳硼烷衍生物3。对此两类化合物进行了核磁、质谱、红外及单晶衍射等表征。化合物1和2中均发现碳硼烷的CH与N形成CH…N氢键和CH…π的弱作用，其中化合物2中，还存在CH…Cl。在巢式化合物3中，发现碳硼烷的CH参与了罕见的CH…HC相互作用。这类反应成功合成了含有B-C、B-Cl、B-P键的碳硼烷衍生物。 |
| 关键词: 碳硼烷 硼位点取代 巢式碳硼烷 BX杂键 |
| 基金项目: 国家自然科学基金（No.21021062）资助项目。 |
| Abstract: The reaction of o-carborane with 4-cyanobenzyl bromide or triphenylphosphine refluxes in toluene in the presence of Lewis acid，in the former reaction, leads to the closo-carborane derivative 1 through the carborane boron substitution cross coupling with the methylene in the 4-cyanobenzyl, and the yield of the product 2 containing B-Cl bond was improved with the increase of the amount of the catalyst. The carborane directly connects with the P atom in triphenylphosphine and loses one B atom, giving rise to nido-carborane derivative 3. All these compounds have been characterized by NMR, MS, IR and X-ray diffraction analysis. Multiple hydrogen bondings CH…N and CH…π interactions were observed in both compounds1 and 2, where carborane CH acts as the hydrogen bond donor. Compound 2 also forms CH…Cl interaction. In compound 3, the carborane CH is involved in the formation of the novel CH…HC hydrogen bonding. These new-type carborane derivatives contain the B-C, B-Cl or B-P bond which are produ ced by the cross coupling reactions. CCDC: 998940, 1; 998941, 2; 998942, 2. |
| Keywords: carborane boron-substitution nido-carborane BX bond |
| 投稿时间：2014-04-24 修订日期：2014-05-08 |
| 摘要点击次数: 1851 |
| 全文下载次数: 1962 |
| 朱琳,蒋其柏,燕红.碳硼烷硼端衍生物的合成与表征[J].无机化学学报,2014,30(10):2246-2251. |
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