金属有的机化学.ppt

Organometallics金属有机化学 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(发烟的) liquid” Contains cacodyloxide(卡可基氧) [(CH3)2As]2O (maldorous 恶臭的） First organometallic compound(化合物). 1827 Zeise’s salt Na[PtCl3C2H4] First olefin(烯烃) complex(络合物、配合物) 1840 R. W. Bunsen continues the study of cacodyl compounds which he names “alkarsines”. 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, 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 (烷基汞) compounds: 2CH3X + 2Na/Hg ? (CH3)2Hg + 2NaX Additionally: (C2H5)4Sn, (CH3)3B (1860). In the following years, alkyl transfer reactions using R2Hg and R2Zn serve in the synthesis of numerous main-group organometallics. Frankland also introduced the concept of valency(“combining power”) and the term organometallic. 1852 K. J. Koning and M. E. Schweizer in Zurich first prepare (C2H5)4Pb from ethyliodide and Na/Pb alloy. In a similar manner, they also obtain (C2H5)4Sb and (C2H5)3Bi. 1859 W. Hallwachs and A. Schafarik generate alkylaluminum iodides: 2Al + 3RI ? R2AlI + RAlI2 1863 C. Friedel and J. M. Crafts prepare Organochlorosilane: SiCl4 + m/2ZnR2 ? RmSiCl4-m + m/2ZnCl2 1866 J. A. Wanklyn develops a method for the synthesis of halide-free magnesium alkyls: (C2H5)2Hg + Mg ? (C2H5)2Mg + Hg 1868 M. P. Schutzenberger obtains [Pt(CO)Cl2]2, first metal carbony(羰基) complex. D. I. Mendeleev uses organometallic compounds as test cases for his periodic table. Ex