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

Reactivity of the 16e CpCo Half-sandwich Complex Containing a Chelating 1,2-Dicarba-closo-dodecaborane-1,2-dithiolate Ligand towards Diynes

含双硫取代碳硼烷二齿配体的半夹心型钴16电子化合物CpCo[S2C2(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。

The reactions of the 16e half-sandwich complex CpCo[S2C2（B10Hlo）] （Col6e） 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（S2C2BloHg）（H2CCPhC =CH） （1）, CpCo （SEC2B10H9）[H2CC （C24H16O4）C =CH] （2）, CpCo（S2C2B10H9）[HECC（C4H2S）Br] （3）, and CpCo（S2C2B,oHg）[H2CC（C4H2S）C =cn] （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（SEC2B10Hg）[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.