1、金属有机化学金属有机化学Organometallics徐崇福徐崇福 1.Introduction（引论）（引论）2.Main-Group Organometallics(主族金属有机化合物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过渡元素金属有机化合物)1.Introduction（引论）（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在金属有
2、机化学领域的历史发展和当前趋势)1760 The cradle(摇篮摇篮)of organometallic chemistry is a Paris military pharmacy(制药厂制药厂).It is there Cadet(军校学员军校学员)works on sympathetic inks（隐显墨水）（隐显墨水）based on cobalt salts.For their preparation,cobalt mineral which contain arsenic(砷砷)was used.As2O3+4CH3COOK “Cadets Fuming liquid”（军学生
3、发烟液体）（军学生发烟液体）Contains cacodyloxide(卡可基氧化物卡可基氧化物)(CH3)2As2O Malodorous（恶臭的）（恶臭的）First organometallic compound(首个有机金属化首个有机金属化合物合物).1827 Zeises salt（蔡斯盐）（蔡斯盐）NaPtCl3C2H4 First olefin complex（首个烯烃配合物）（首个烯烃配合物）.1840 R.W.Bunsen（本生）（本生）continues the study of cacodyl compounds which he names“alkarsines”（卡可
4、基酸氧化物）（卡可基酸氧化物）.The weakness of As-As bond in molecules of the type R2As-AsR2 led to a profusion(丰富丰富)of derivatives(衍生物衍生物)like(CH3)2AsCN whose taste is checked by Bunsen！1849 E.Frankland（弗兰克兰）（弗兰克兰）,student of Bunsen,attepts the preparation of an“ethyl radical”(乙基自由基乙基自由基).(cacodyl as well was tak
5、en to be a radical).1852 Frankland prepares the important alkylmercury compounds(烷基汞化合物烷基汞化合物):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）（烷基转移反应）using R2Hg and R2Zn serve in the synthesis of numerous main-group organometall
6、ics（众多的主族金属有机化合物的（众多的主族金属有机化合物的合成）合成）.Frankland also introduced the concept of valency（化合价概念）（化合价概念）“combining power”and the term organometallic(有机金属主干有机金属主干).1852 K.J.Konig（康尼）（康尼）and M.E.Schweizer in Zurich（苏黎世）（苏黎世）first prepare(C2H5)4Pb from ethyliodide（乙基碘）（乙基碘）and Na/Pb alloy（合（合金）金）.In a simi
7、lar manner,they also obtain(C2H5)4Sb and(C2H5)3Bi.1859 W.Hallwachs and A.Schafarik generate alkylaluminum（烷基铝）（烷基铝）iodides:2Al +3RI R2AlI +RAlI2 1863 C.Friedel（弗瑞德）（弗瑞德）and J.M.Crafts（克（克莱福特）莱福特）prepare Organochlorosilane（有机氯（有机氯硅烷）硅烷）:SiCl4+m/2ZnR2 RmSiCl4-m+m/2ZnCl2 1866 J.A.Wanklyn develops a met
8、hod for the synthesis of halide-free magnesium alkyls（不含（不含卤素的烷基镁）卤素的烷基镁）:(C2H5)2Hg+Mg (C2H5)2Mg+Hg 1868 M.P.Schutzenberger obtains Pt(CO)Cl22,first metal carbonyl complex（首个金属羰基配（首个金属羰基配合物）合物）.D.I.Mendeleev（门捷列夫）（门捷列夫）uses organometallic compounds as test cases（试验例（试验例证）证）for his periodic table（周期表
9、）（周期表）.KnownpredictedfoundfounderSi(C2H5)4Eka-Si(C2H5)4类类-Si(C2H5)4Sn(C2H5)4d=0.96d=0.99C.Winkler1887bp:160oCbp:163.5oC 1890 L.Mond（蒙德）（蒙德）:Ni(CO)4,first binary metal carbonyl（首个二元金属羰基化合物）（首个二元金属羰基化合物）,used in a commercial process for refining nickel（镍的商业精炼过程）（镍的商业精炼过程）.Mond is the founder of the En
10、glish company ICI(Imperial Chemical Industries 帝国化工帝国化工)as well as a renowned collector and patron of the arts（著名的艺术收（著名的艺术收集家及恩主）集家及恩主）.1899 P.Barbier（巴比）（巴比）replaces Mg for Zn in reactions with alkyl iodides:CH3CH3CCHH2CCOCH31.CH3I,Mg2.H2OCH3CH3CCHH2CCOHCH3CH3 Explored in more detail by Barbiers s
11、tudent V.Grignard（格利雅）（格利雅）(Nobel prize 1912 shared with P.Sabatier）.Although less sensitive than ZnR2,RMgX is more potent alkyl group transfer reagent(强有力的烷基迁移剂强有力的烷基迁移剂).1901 L.F.S.Kipping prepares(C6H5)2SiO,suspects its high molecularity（高分子性）（高分子性）,and calls the material diphenylsilicone（二苯基硅（二苯
12、基硅酮）酮）.1909 W.J.Pope:formation of(CH3)3PtI,first s s-organotransition-metal compound.1909 P.Ehrlich，inventer of chemotherapy化疗化疗法发明者法发明者,Nobel prize 1908 introduces Salvarsan(洒尔佛散洒尔佛散)for the treatment of syphilis(梅毒梅毒)O2NHOAsO(OH)2Na2S2O4H2OO2NHOAsn nn=5,6,7 Salvarsan 1917 W.Schlenk（舒兰克）（舒兰克）:Lithi
13、um alkyls via transalkylation(经由烷基烷基转换得到烷基锂经由烷基烷基转换得到烷基锂).2Li +R2Hg 2LiR +Hg 2EtLi +Me2Hg 2MeLi +Et2Hg 1919 F.Hein from CrCl3 and PhMgBr synthesizes polyphenylchromium compounds（聚苯基铬化（聚苯基铬化合物）合物）,now known to be sandwich complexes（三明治化合物）（三明治化合物）.1922 T.Midgley and T.A.Boyd introduces Pb(C2H5)4 as a
14、n antiknock additive in gasoline.1928 W.Hieber inaugurates his systematic study of metal carbonyls（开始他的金属羰基化合物的（开始他的金属羰基化合物的系统研究）系统研究）:Fe(CO)5+H2NCH2CH2NH2 (H2NCH2CH2NH2)Fe(CO)3+2CO Fe(CO)5+X2 Fe(CO)4X2+CO 1929 F.A.Paneth 潘纳思）潘纳思）generates alkyl radicals through PbR4 pyrolysis(通过通过PbR4的热解的热解产生烷基自由基产
15、生烷基自由基),radical identification by means of their ability to cause the transport of a metallic mirror（由它们能引起金属银镜传输的能力进行（由它们能引起金属银镜传输的能力进行自由基鉴定）自由基鉴定）.Paneth thus reaches a goal set by Frankland in 1849（于是，潘纳思就达到了（于是，潘纳思就达到了1849年由弗兰克兰设定的目标）年由弗兰克兰设定的目标）.1930 K.Ziegler（齐格勒）（齐格勒）encourages more extensive
16、 use of organolithium compounds in synthesis by developing a simpler way of preparation（通过开发出一个更简便的制备方法（通过开发出一个更简便的制备方法激励了有机锂化合物在合成中更加广泛的应用）激励了有机锂化合物在合成中更加广泛的应用）.PhCH2OMe+2Li PhCH2Li+MeOLi(ether cleavage，醚裂解，醚裂解)H.Gilman:RX+2Li RLi+LiX(procedure used today)1931 W.Hieber prepares Fe(CO)4H2,the first
17、transition-metal hydride complex(首个过渡金属首个过渡金属负氢离子配合物负氢离子配合物).1938 O.Roelen discovers hydroformylation(加氢加氢甲酰化甲酰化)，(the oxo process，羰基合成法羰基合成法).CH2=CH2+CO+H2Co2(CO)890-150 100-400 barCH3CH2COH 1939 W.Reppe（雷帕）（雷帕）starts work on the transition-metal catalyzed reactions of acetylene(开始了由过渡金属催化下乙炔反应的研究工
18、作开始了由过渡金属催化下乙炔反应的研究工作).HCCH4Ni(CN)2/CaC2/THF80-120,15 bar70%1943 E.G.Rochow:Cu-Cat.,300 2CH3Cl+Si-(CH3)2SiCl2+This“direct synthesis”triggers large scale production and use of silicones（这种（这种“直接的合直接的合成成”引发了硅酮的大规模生产和使用）引发了硅酮的大规模生产和使用）.Preliminary work by R.Muller(Radebeul near Dresden)was interrupted
19、by the Second World War.（R Muller的前期工作为第二次世界大战所的前期工作为第二次世界大战所打断）打断）1951 P.Pauson(GB)and S.A.Miller(USA)obtain ferrocene(二茂铁二茂铁)(C5H5)2Fe,the first proven sandwich complex（首个得到确切证实三（首个得到确切证实三明治配合物）明治配合物）.Fe 1953 G.Wittig（维悌希）（维悌希）discovers the reaction bearing his name（发现以它的名字命名的反应）（发现以它的名字命名的反应）OCPh
20、PhPh3PCH2+OPPh3+H2CCPhPh(CO)5W=CPhPh+Ph3P=CH2(CO)5WPPh3+H2C=CPhPh 1955 E.O.Fischer（费歇尔）（费歇尔）:rational synthesis of bis(benzene)chromium(C6H6)2Cr（二苯铬的（二苯铬的理性化合成）理性化合成）.1955 K.Ziegler（齐格勒）（齐格勒）,G.Natta（纳塔）（纳塔）:polyolefins from ethylene and propylene,respectively,in a low pressure process employing mix
21、ed metal catalysts(transition-metal halide/AlR3).（使用混合金属催化剂（使用混合金属催化剂 t-MX/AlR3，在低，在低压过程中分别从乙烯和丙烯合成聚烯烃）压过程中分别从乙烯和丙烯合成聚烯烃）1956 H.C.Brown（布朗）（布朗）:hydroborane(氢硅氢硅烷烷).1959 J.Smodt,W.Hafner:preparation of(C3H5)PdCl2,installation(建立建立)of the field of p p-allyl transition-metal complexes（创立了离域化（创立了离域化p p-
22、烯丙基过渡金属配合物领域）烯丙基过渡金属配合物领域）.M 3-allyl(C3H5)1959 R.Crigee stabilization(稳定稳定)of cyclobutadiene(环丁二烯环丁二烯)by complexation in(C4Me4)NiCl22 veryfying a prediction by H.C.Longuet-Higgins and L.Orgel(1956)（通过对（通过对(C4Me4)NiCl22的络合将环丁二烯稳定化，证实的络合将环丁二烯稳定化，证实了了LonguetHiggins和和Orgel在在1956年的一个预年的一个预言）言）.1960 M.F.H
23、awthorne:carboranes(碳硅烷碳硅烷).1961 L.Vaska:(PPh3)2Ir(CO)Cl reversibly binds O2（(PPh3)2Ir(CO)Cl可逆地结合可逆地结合O2）.1963 Nobel prize to K.Ziegler and G.Natta.1964 E.O.Fischer:(CO)5WC(OMe)Me,first carbene complex（首个卡宾配合物）（首个卡宾配合物）.1965 G.Wilkinson（威尔金森）（威尔金森）,R.S.Coffey（科菲）（科菲）:(PPh3)3RhCl acts as a homogeneou
24、s catalyst in the hydrogenation of alkenes（(PPh3)3RhCl在烯烃的氢化中作用为均相催化在烯烃的氢化中作用为均相催化剂剂).1968 A.Streitwieser:preparation of uranocene(制备二茂铀制备二茂铀),(C8H8)2U.1969 P.L.Timms:synthesis of organotransition-metal complexes by means of metal-atom ligand-vapor cocondensation(通过金属原子配体蒸汽共通过金属原子配体蒸汽共凝聚合成过渡金属配合物凝聚合
25、成过渡金属配合物).1970 G.Wilkinson:kinetically inert transition-metal alkyls through blockage of b b-elemination(通过阻断通过阻断b b消除得到动力学惰性的过渡金属烷消除得到动力学惰性的过渡金属烷基化合物基化合物).1972 H.Werner（维尔纳）（维尔纳）:(C5H3)3Ni2+,first triple-decker sandwich complex（首个三层三明（首个三层三明治配合物）治配合物）.1973 E.O.Fischer：ICO4CrCR,first carbyne complex
26、（首个卡拜配合物）（首个卡拜配合物）.1973 Nobel prize to E.O.Fischer and G Wilkinson.1976 Nobel prize to W.N.Lipscomb:theoretical and experimental clarification of structure and bonding in boranes（硼烷结构和价键理论和经（硼烷结构和价键理论和经验的澄清）验的澄清）.1979 Nobel prize to H.C.Brown and G.Wittig:application of organoboranes and methyleneph
27、osporanes,respectively,in organic synthesis（有机硼烷和亚甲基磷烷分别在有机合（有机硼烷和亚甲基磷烷分别在有机合成中的应用）成中的应用）.1981 R.West：(1,3,5-Me3C6H2)4Si2,first stable compound with=Si=Si=double bond（首个具有（首个具有硅硅双键的稳定化合物）硅硅双键的稳定化合物）.1981 Nobel prize to R.Hoffman（霍夫曼）（霍夫曼）and K.Fukui（福井谦一）（福井谦一）:semiempirical MO-concept in a unified
28、discussion of structure and reactivity of inorganic,organic and organometallic molecules,isolobal analogies(半半经验分子轨道概念在无机，有机及金属有机分子经验分子轨道概念在无机，有机及金属有机分子结构和反应性的统一讨论，等叶类比结构和反应性的统一讨论，等叶类比).1983 R.G.Bergman,W.A.G.Graham:intermolecular reactions of organotransition-metal compounds with alkanes，C-H activa
29、tion（有机过渡金属化合物与烷烃的分子间反应，碳（有机过渡金属化合物与烷烃的分子间反应，碳氢键活化）氢键活化）.1983 Nobel Prize to Henry Taube for his work on the mechanisms of electron transfer reactions,especially in metal complexes.（尤其在金属配合物中，电子转移反应机理）（尤其在金属配合物中，电子转移反应机理）1994 Nobel Prize to George A.Olah for his contribution to carbocation chemistry
30、.（对碳正离子的贡献）（对碳正离子的贡献）1996 Nobel Prize to Robert F.Curl Jr.,Sir Harold W.Kroto and Richard E.Smalley for their discovery of fullerenes.（富勒烯的发现）（富勒烯的发现）2001 The Nobel Prize was awarded with one half jointly to:William S.Knowles and RyoJi Noyori for their work on chirally catalyzed hydrogenation reacti
31、ons（手性催化氢化反应工作）（手性催化氢化反应工作）And the other half to:K.Barry Sharpless for his work on chirally catalyzed oxidation reactions.（手性催化氧化工作）（手性催化氧化工作）HArNHAcHOOCH2,Chiral catalystC*HOOCNHAcHCHHArC*HOOCNHAcArHHCH+973:P*P*Rh+PhPhOMeMeOPhPhSSCatalyst:Ar=3,4-C6H3(OH)2Monsanto(Knowles,1977)The chiral amino acid
32、L-Dopa is aneffective medicine in the treatment ofParkinsons diseasePPh2PPh2PPh2PPh2(R)-BINAP(S)-BINAP-Super chiral ligand BINAP(Ryoji Noyori 野野依依良良治治,1980)-Chiral compouds without chiral centers;-Posses C2 symmetric axis;-Two naphthalene rings are not in the same plane,they can rotate certain degre
33、e to accommodate variety of substrates;-Two big naphthalene rings supply sufficient chiral barrier.2010 Nobel prize was awarded jointly to Richard F.Heck,Ei-Ichi Negishi,and Akira Suzuki for palladium-catalyzed cross couplings in organic synthesis.（在有机合成中的钯催化交联）（在有机合成中的钯催化交联）Br+CO2Me+Et3N1%Pd(OAc)22
34、%PPh3,100oCCO2Me-Et3NHBrThe catalyst is a Pd0 complex,formed in situ from Pd(OAc)2,Et3N and PPh3催催化化剂剂是是Pd0配配合合物物，从从Pd(OAc)2即即席席生生成成H Exercises 1:1.What was the first olefin complex?2.In what year did P.Ehrlich won Nobel prize and what was his invention?3.What was K.Ziegler and G.Nattas major discov
35、ery?4.What was G.Wilkinsons discovery?5.What did W.N.Lipscomb win Nobel prize for?6.For what did G.Wittig win Nobel prize?7.What were R.Hoffman and K.Fukui awarded Nobel prize for?8.What project R.G.Bergman and W.A.G.Graham work for?9.What have William S.Knowles and RyoJi Noyori accomplished for the
36、ir Nobel prize?10.What kind of achievement does the Nobel prize award for the year 2010?1.2 Classification of Organometallic Compounds（金属有机化合物分类）（金属有机化合物分类）Organometallic compounds are defined as materials which possess direct,more or less polar bonds Md d+-Cd d-between metal and carbon atoms.（金属有机化
37、合物定义为在金属和碳原子之间具（金属有机化合物定义为在金属和碳原子之间具有直接的，或多或少极性有直接的，或多或少极性Md d+-Cd d-键的材料）键的材料）The designation of s s-,p p-,d d-bonds s-,p p-,d d-键的指定键的指定Overlap重合重合Number of nodal planes节面数节面数 Bond type价键类型价键类型Example实例实例 0 s s 1 p p(CO)5Cr=CR2 2 d d+BCH3R4ReReR41.3 Energy,Polarity and Reactivity of M-C Bond 金属金属-
38、碳键的能量，极性和反应性碳键的能量，极性和反应性 It is important to distinguish（区别）（区别）between thermodynamic(热力学热力学)(stable,unstable)and kinetic(动力学动力学)(inert,labile)1.3.1 Stability of Main-group Organometallics（主族金属有机化合物的稳定性）（主族金属有机化合物的稳定性）Compared with the strengths of M-N,M-O and M-Halogen bond,M-C bonds must be deemed
39、weak（与金属（与金属-氮，金属氮，金属-氧以及金属氧以及金属-卤素键的卤素键的强度相比，金属强度相比，金属-碳键必然被认为是弱的）碳键必然被认为是弱的）.M-C bond energies cover a wide range（金属（金属-碳碳键能覆盖广阔的范围）键能覆盖广阔的范围）Compound(CH3)3B(CH3)3As (CH3)3Bi E(M-C)365229 141 kJ/molstrongmedium weak The mean bond energy E(M-C)with a main-group decreases with the increasing atomic
40、number（对于主族来说平均键能（对于主族来说平均键能E（M-C）随着）随着原子序数的增加而下降）原子序数的增加而下降）.Ionic bonds are encountered if M is particularly electropositive and/or the carbanion is especially stable（如果金属特别电正性或者碳负离子特别（如果金属特别电正性或者碳负离子特别稳定，将出现离子键）稳定，将出现离子键）.Examples:Na+C5H5-,K+CPh3-,Na+CCR-Multicenter bonding(“electron deficient bo
41、nd”)arises if the valence shell of M is less than half filled and the cation Mn+is srongly polarizing(possesses a large charge/radius ratio)（如果金属（如果金属价层少于半满或者正离子强烈极化，即电荷价层少于半满或者正离子强烈极化，即电荷/半半径比很大，将出现多中心键）径比很大，将出现多中心键）.Examples:(LiCH3)4,Be(CH3)2n,Al(CH3)321.3.2 Lability of Main-Group Organometallics主
42、族金属有机化合物的活跃性主族金属有机化合物的活跃性 All organometallics are thermodynamically unstable with respect to oxidation to MOn,H2O and CO2.Nevertheless,large differences in the ease of handling of organometallics are encountered which may be traced back to differences in kinetic inertness(同有机化合物相同有机化合物相比，所有金属有机化合物热力
43、学不稳定，然而处比，所有金属有机化合物热力学不稳定，然而处理它们的难易却相差很大，这要追索到它们动力理它们的难易却相差很大，这要追索到它们动力学惰性差异）。学惰性差异）。Heat of combustion燃烧热燃烧热Thermodynamics热力学热力学Property性质性质Kinetics动力学动力学Zn(C2H5)2-1920kJ/molunstablePyrophoric(引火的引火的)Labile(活性的活性的)Sn(CH3)4-3590kJ/molunstableAirstable空气稳定空气稳定Inert(惰性的惰性的)In air在空气中在空气中In water在水中在水中
44、Relavant factors相关因素相关因素Me3InPyrophoric起火起火Hydrolysed水解水解Electron gap at In,highly bond polarity.铟有电子缺铟有电子缺口，高度键极性口，高度键极性Me4SnInert 惰性惰性Inert惰性惰性Sn shielded well,low bond polarity.锡得到很好屏蔽，低锡得到很好屏蔽，低键极性。键极性。Me3SbpyrophoricInert惰性惰性Free electron pair on Sb.在锑上有一在锑上有一对自由电子对自由电子In airIn waterRelavant fa
45、ctorsMe3B pyrophoricinertElectron gap at B is closed by means of hyperconjugation,low bond polarityMe3Al pyrophoric hydrolyzed Electron gap at Al in the monomer,nucleophilic attack via Al(3d)in the dimer,high bond polarity.In airIn waterRelavant factorsSiH4pyrophoric hydrolyzed Si shielded ineffecti
46、vely,attack of O2 and nucleophiles via Si(3d).SiCl4inerthydrolyzed Si relatively electron poor,high polarity of Si-Cl bonds,nucleophilic attack via Si(3d).SiMe4inertinertSi shielded effectively,low polarity of Si-C bonds.1.4 Concise introduction of nomenclature in elements and chemical compounds元素及其
47、化合物的命名简介元素及其化合物的命名简介1.4.1 Nomenclature of organic compounds有机化合物的命名有机化合物的命名H3CCCCH3CH3HHH2-methylbutanenumber&prefixPosition&number of carbons in branchrootsuffixnumber of carbonsin backbone chaindesignatethe functional groupInternational Union of Pure and Applied Chemistry(IUPAC)国国际际纯纯粹粹和和应应用用化化学学协
48、协会会 Names for the root designating carbon numbers in the backbone chain 用于表达主链碳数目的根名用于表达主链碳数目的根名C-numbersrootC-numbers rootOnemeth-twoeth-Threeprop-fourbut-Fivepent-sixhex-Sevenhept-eightoct-Ninenon-tendec-Elevenundec-twelvedodec-Thirteentridec-fourteentetradec-Fifteenpentadec-twentyeicos-Twenty one
49、heneicos-twenty two docos-Thirtytriacont-Systematic names,common names and abbreviations for some groups 一些基团的系统名，一些基团的系统名，俗名以及缩写俗名以及缩写Groupsys.name com.nameabbrev.基团基团系统命名系统命名 普通名称普通名称缩写缩写CH3-methylMeCH3CH2-ethylEtCH3(CH2)2-propylPr(CH3)2CH-1-methylethyl isopropyli-PrCH3(CH2)3-butylBu(CH3)3C-1,1-di
50、methylethyl-ter-butylt-BuC6H5-phenylPhC6H5CH2-phenylmethyl-benzylBezNames of common functional groups(常见官能团的名称常见官能团的名称)FormulaNamePrefixSufix RHAlkanealkyl-aneRCH=CH2Alkenevinyl-eneRCCHAlkyne-yneArHArenephenyl-benzeneRXAlkyl halidehalo-halideROHAlcoholhydroxo-olROREtheralkoxo-etherRNH2Amineamino-ami
