基于B-H键的活化对含B-C、B-Cl、B-P键的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

作　　者：朱琳[1] 蒋其柏[1] 燕红[1] 

机构地区：[1]配位化学国家重点实验室,南京大学化学化工学院,南京210093

出　　处：《无机化学学报》2014年第10期2246-2251,共6页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.21021062)资助项目

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。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 2containing 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 compounds 1 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 produced by the cross coupling reactions. CCDC： 998940, 1;998941, 2;998942, 2.

关 键 词：碳硼烷 硼位点取代 巢式碳硼烷 BX杂键 

分 类 号：O613.81[理学—无机化学]