| 含碳硼烷半夹心型钴硫16电子化合物与二炔烃的反应性研究 |
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| 引用本文： | 徐智伟,韩 磊,杨震洲,沈旭杰,燕 红.含碳硼烷半夹心型钴硫16电子化合物与二炔烃的反应性研究[J].无机化学学报,2011,27(9):1669-1674. |
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| 作者姓名： | 徐智伟 韩 磊 杨震洲 沈旭杰 燕 红 |
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| 作者单位： | 南京大学化学化工学院,南京,210093 |
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| 基金项目： | 国家自然科学基金(No.20925104,No.21021062); 江苏省自然科学基金(No.BK2010052); 教育部博士点基金(No.20090091110015)资助项目 |
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| 摘 要： | 含双硫取代碳硼烷二齿配体的半夹心型钴16电子化合物CpCoS2C2(B10H10)](Co16e)分别与1,4-二乙炔基苯(L1)、(S)-2,2′-二乙酰氧基-6,6′-二乙炔基-1,1′-联萘(L2)、2-溴-5-乙炔基噻吩(L3)和2,5-二乙炔基噻吩(L4)反应,分别得到18电子单核化合物CpCo(S2C2B10H9)(H2CCPhC≡CH)(1),CpCo(S2C2B10H9)H2CC(C24H16O4)C≡CH](2),CpCo(S2C2B10H9)H2CC(C4H2S)Br](3),和CpCo(S2C2B10H9)H2CC(C4H2S)C≡CH](4)。化合物1～4的结构中都发生了金属诱导B-H键活化并生成了新的C-B键。在Co16e与L4的反应中,还得到了两分子炔烃以头对头二聚插入到金属中心的18电子化合物CpCo(S2C2B10H9)HC≡C(C4H2S)C=CH-CH=C(C4H2S)C≡CH](5)。上述化合物通过NMR、IR、MS、元素分析等方法进行表征。
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| 关 键 词： | 钴硫16e化合物 二炔烃 B-H键活化 |
Reactivity of the 16e CpCo Half-sandwich Complex Containing a Chelating 1,2-Dicarba-closo-dodecaborane-1,2-dithiolate Ligand towards Diynes |
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| XU Zhi-Wei,HAN Lei,YANG Zhen-Zhou,SHEN Xu-Jie and YAN Hong.Reactivity of the 16e CpCo Half-sandwich Complex Containing a Chelating 1,2-Dicarba-closo-dodecaborane-1,2-dithiolate Ligand towards Diynes[J].Chinese Journal of Inorganic Chemistry,2011,27(9):1669-1674. |
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| Authors: | XU Zhi-Wei HAN Lei YANG Zhen-Zhou SHEN Xu-Jie and YAN Hong |
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| Institution: | State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China,State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China,State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China,State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China and State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China |
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| Abstract: | The reactions of the 16e half-sandwich complex CpCoS2C2(B10H10)](Co16e) with 1,4-diethynylbenzene(L1),3′,6-diethynyl-1,1′-binaphthyl-2,7′-diyl diacetate(L2),2-bromo-5-ethynylthiophene(L3),and 2,5-diethynyl-thiophene(L4) lead to 18e mononuclear complexes CpCo(S2C2B10H9)(H2CCPhC≡CH)(1),CpCo(S2C2B10H9)H2CC(C24H16O4)C≡CH](2),CpCo(S2C2B10H9)H2CC(C4H2S)Br](3),and CpCo(S2C2B10H9)H2CC(C4H2S)C≡CH](4),respe-ctively.In all of the products the metal-induced B-H activation has occurred that leads to a new C-B bond.In the case of L4,CpCo(S2C2B10H9)HC≡C(C4H2S)C=CH-CH=C(C4H2S)C≡CH](5) is generated as well,in which alkyne is twofold inserted into a Co-S bond.All these products 1～5 have been characterized by NMR,IR,mass spectro-metry and elemental analysis. |
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| Keywords: | 16e cobalt complex diyne B-H activation |
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