2010年无机化学课件-第5章 非金属原子簇化合物.pptVIP

第5章 非金属原子簇化合物 一. 硼烷(Borane)的组成 二. 硼烷中的化学键 (定域) 三. 硼烷的骨架电子对规则(Wade’s rule) 五. 碳硼烷及金属硼烷衍生物 六. 富勒烯(Fullerenes)化学 Using mass spectrometry, discrete peaks appeared corresponding to molecules with the exact mass of sixty or seventy or more carbon atoms. In 1985, Harold Kroto (then of the University of Sussex), James R. Heath, Sean OBrien, Robert Curl and Richard Smalley, from Rice University, discovered C60, and shortly thereafter came to discover the fullerenes. Kroto, Curl, and Smalley were awarded the 1996 Nobel Prize in Chemistry for their roles in the discovery of this class of molecules. C60 and other fullerenes were later noticed occurring outside the laboratory (e.g., in normal candle soot). 七. 碳纳米管( carbon nanotube) C60 Ih C70 D5d 如何确认C60 的结构？ 13C NMR spectrum of the purified C60 , reported by Kroto et al. (Taylor, 1990). The NMR spectrum contained a single peak at 142.7, as expected for the highly symmetrical truncated icosahedron structure in which all carbons are identical Definitive proof for the structure of C60 came in 1991 when Joel Hawkins (Univ. of California-Berkeley) synthesized and crystallized an osmium derivative of (C60)OsO4 (4-tert-butylpyridine)2. Single crystal X-ray analysis of this compound yielded the first atomic-resolution picture of the carbon framework of C60 (C 60 )OsO4 (4-叔丁基吡啶)2 S0.9p2.28杂化，30个6/6双键，截顶20面体（B12） 热力学稳定性比石墨差可被还原 和自由基、亲核试剂加成和化学修饰 制备富勒烯的电弧炉 不同条件下合成的富勒烯的质谱图(He的压力不同和反应时间不同） 富勒烯及碳纳米管的主要研究方面 1. 制备和分离 理论计算 化学修饰 a. 富勒烯的超导化合物 b. 环加成反应(有机反应), C60与氨基酸酯的加成 c. 富勒烯配合物 d. 富勒烯包合物的研究 4. 碳纳米管的制备 153 K. C60 crystallizes in a face centered cubic， space group Pa3. 富勒烯的金属化合物, K3C60 , Rb3C60, Cs3C60 , KxC60 超导温度18K C60以面心立方密堆积, K, Rb, Cs 填充全部八面体 和四面体空隙 富勒烯的衍生物 Polymeric fullerene chains in RbC60 2. 金属富勒烯包合物 （EMF, endohedral metallofullerenes) 单金属: La@82 双金属: Sc2@82 三金属: Sc3@82 杂原子: Sc3N@80 3. 富勒烯的金属配合物 [Os(O)4(py)2(C60)] (eta2-C70-Ful