金属有机化学2011

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1、金属有机化学Organometallics徐崇福1.Introduction（引论）2.Main-GroupOrganometallics(主族金属有机化合物)3.OrganometallicCompoundsoftheTransitionElements(过渡元素金属有机化合物)1.Introduction（引论）1.1HistoricalDevelopmentandCurrentTrendsinOrganometallicChemistry(在金属有机化学领域的历史发展和当前趋势)1760Thecradle(摇篮)oforganometa

2、llicchemistryisaParismilitarypharmacy(制药厂).ItisthereCadet(军校学员)worksonsympatheticinks（隐显墨水）basedoncobaltsalts.Fortheirpreparation,cobaltmineralwhichcontainarsenic(砷)wasused.As2O3+4CH3COOK“Cadet’sFumingliquid”（军学生发烟液体）Containscacodyloxide(卡可基氧化物)[(CH3)2As]2OMalodorous（恶臭的）Fir

3、storganometalliccompound(首个有机金属化合物).1827Zeise’ssalt（蔡斯盐）Na[PtCl3C2H4]Firstolefincomplex（首个烯烃配合物）.1840R.W.Bunsen（本生）continuesthestudyofcacodylcompoundswhichhenames“alkarsines”（卡可基酸氧化物）.TheweaknessofAs-AsbondinmoleculesofthetypeR2As-AsR2ledtoaprofusion(丰富)ofderivatives(衍生物)like

4、(CH3)2AsCNwhosetasteischeckedbyBunsen！1849E.Frankland（弗兰克兰）,studentofBunsen,atteptsthepreparationofan“ethylradical”(乙基自由基).(cacodylaswellwastakentobearadical).1852Franklandpreparestheimportantalkylmercurycompounds(烷基汞化合物):2CH3X+2Na/Hg(CH3)2Hg+2NaXAdditionally:(C2H5)4Sn,(CH3)

5、3B(1860).Inthefollowingyears,alkyltransferreactions（烷基转移反应）usingR2HgandR2Znserveinthesynthesisofnumerousmain-grouporganometallics（众多的主族金属有机化合物的合成）.Franklandalsointroducedtheconceptofvalency（化合价概念）“combiningpower”andthetermorganometallic(有机金属主干).1852K.J.Konig（康尼）andM.E.Schweiz

6、erinZurich（苏黎世）firstprepare(C2H5)4Pbfromethyliodide（乙基碘）andNa/Pballoy（合金）.Inasimilarmanner,theyalsoobtain(C2H5)4Sband(C2H5)3Bi.1859W.HallwachsandA.Schafarikgeneratealkylaluminum（烷基铝）iodides:2Al+3RIR2AlI+RAlI21863C.Friedel（弗瑞德）andJ.M.Crafts（克莱福特）prepareOrganochlorosilane（有机氯硅

7、烷）:SiCl4+m/2ZnR2RmSiCl4-m+m/2ZnCl21866J.A.Wanklyndevelopsamethodforthesynthesisofhalide-freemagnesiumalkyls（不含卤素的烷基镁）:(C2H5)2Hg+Mg(C2H5)2Mg+Hg1868M.P.Schutzenbergerobtains[Pt(CO)Cl2]2,firstmetalcarbonylcomplex（首个金属羰基配合物）.D.I.Mendeleev（门捷列夫）usesorganometalliccompoundsastestc

8、ases（试验例证）forhisperiodictable（周期表）.KnownpredictedfoundfounderSi(C2H5