金属有机化学2011课件.ppt

金属有机化学Organometallics 徐崇福 1. Introduction（引论） 2. Main-Group Organometallics(主族金属有机化合物) 3. Organometallic Compounds of the Transition Elements(过渡元素金属有机化合物) 1. Introduction（引论） 1.1 Historical Development and Current Trends in Organometallic Chemistry (在金属有机化学领域的历史发展和当前趋势) 1760 The cradle(摇篮) of organometallic chemistry is a Paris military pharmacy(制药厂). It is there Cadet(军校学员) works on sympathetic inks（隐显墨水）based on cobalt salts. For their preparation, cobalt mineral which contain arsenic(砷) was used. As2O3 + 4CH3COOK ? “Cadet’s Fuming liquid”（军学生发烟液体） Contains cacodyloxide (卡可基氧化物) [(CH3)2As]2O Malodorous （恶臭的） First organometallic compound (首个有机金属化合物). 1827 Zeise’s salt（蔡斯盐） Na[PtCl3C2H4] First olefin complex（首个烯烃配合物）. 1840 R. W. Bunsen（本生） continues the study of cacodyl compounds which he names “alkarsines”（卡可基酸氧化物）. The weakness of As-As bond in molecules of the type R2As-AsR2 led to a profusion (丰富) of derivatives (衍生物) like (CH3)2AsCN whose taste is checked by Bunsen！ 1849 E. Frankland（弗兰克兰）, student of Bunsen, attepts the preparation of an “ethyl radical”(乙基自由基). (cacodyl as well was taken to be a radical). 1852 Frankland prepares the important alkylmercury compounds (烷基汞化合物) : 2CH3X + 2Na/Hg ? (CH3)2Hg + 2NaX Additionally: (C2H5)4Sn, (CH3)3B (1860). In the following years, alkyl transfer reactions （烷基转移反应）using R2Hg and R2Zn serve in the synthesis of numerous main-group organometallics（众多的主族金属有机化合物的合成）. Frankland also introduced the concept of valency（化合价概念）“combining power” and the term organometallic (有机金属主干). 1852 K. J. Konig （康尼）and M. E. Schweizer in Zurich （苏黎世）first prepare (C2H5)4Pb from ethyliodide （乙基碘）and Na/Pb alloy（合金）. In a similar manner, they also obtain (C2H5)4Sb and (C2H5)3Bi. 1859 W. Hallwachs and A. Schafarik generate alkylaluminum（烷基铝） iodides: 2Al + 3RI ? R2AlI + RAlI2 1863 C. Friedel （弗瑞德）and J. M. Crafts（克莱福特） prepare Organochlorosilane（有机氯硅烷）: SiCl4 + m/2ZnR2 ? RmSiCl4-m + m/2ZnCl2 1866 J. A. Wanklyn develops a method fo