The reactions of the 16e half-sandwich complex CpCo[S2C2(B10H10)] (Col6e) with 1,4-diethynylbenzene (LI), 3',6-diethynyl-l,l'-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), respectively. 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.%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≡C H] (5).上述化合物通过NMR、IR、MS、元素分析等方法进行表征.
展开▼
