金属有机课件Class No 1

1、金属有机化学金属有机化学- 金属参与的现代有机合成反应金属参与的现代有机合成反应王王 磊磊淮北师范大学淮北师范大学Definition of this course: C(H)-Metal bond is formed during/or after the reaction. Main Textbook:Prof. Ma Shengming (SIOC, AC, CN) 广东科技出版社广东科技出版社, 第二版第二版, 2003无机化学有机化学金属有机碳（氢)金属键的形成和反应金属元素占所有元素的约80 诺贝尔化学奖(1) 1912年V. Grignard(2) 1963年Ziegler和Na

2、tta(3) 1973年E. O. Fisher和G. Wilkinson(the chemistry of sandwich compounds)(4) 1976年W. N. Lipscomb(5) 1979年H. C. Brown 和 G. Wittig (6) The Nobel Prize in Chemistry 2001 for their work on chirally catalysed hydrogenation reactionsWilliam S. Knowles Ryoji Noyori St. Louis, MO, USA Nagoya University, Ch

3、ikusa, Nagoya, Japan 1938for his work on chirally catalysed oxidation reactions K. Barry Sharpless 1941 The Scripps Research Institute La Jolla, CA, USA 1917 -www.nobel.se(7) The Nobel Prize in Chemistry 2005In 1971 Yves Chauvin was able to explain in detail how metatheses reactions function and wha

4、t types of metal compound act as catalysts in the reactions. Now the recipe was known. The next step was, if possible, to develop the actual catalysts.Richard Schrock was the first to produce an efficient metal-compound catalyst for methasesis. This was in 1990. Two years later Robert Grubbs develop

5、ed an even better catalyst, stable in air, that has found many applications.Metathesis is used daily in the chemical industry, mainly in the development of pharmaceuticals and of advanced plastic materials. 2004年年5月月17日日19日，日，Grubbs作了题为作了题为“The Synthesis of Large and Small Molecules Using Olefin Met

6、athesis”的报告的报告Metathesis a change-your-partners danceThis years Nobel Prize Laureates in chemistry have made metathesis into one of organic chemistrys most important reactions. Fantastic opportunities have been created for producing many new molecules pharm-aceuticals, for example. Imagination will

7、soon be the only limit to what molecules can be built! Organic substances contain the element carbon. Carbon atoms can form long chains and rings, bind other elements such as hydrogen and oxygen, form double bonds, etc. 在宣布仪式上，诺贝尔化学奖评委会主席佩尔在宣布仪式上，诺贝尔化学奖评委会主席佩尔阿尔伯格阿尔伯格将烯烃复分解反应描述为将烯烃复分解反应描述为“交换舞伴的舞蹈交换

8、舞伴的舞蹈”。他亲。他亲自走出讲台，邀请身边的皇家科学院教授和两位女工自走出讲台，邀请身边的皇家科学院教授和两位女工作人员一起在会场中央为大家表演烯烃复分解反应的作人员一起在会场中央为大家表演烯烃复分解反应的含义。最初两位男士是一对舞伴，两位女士是一对舞含义。最初两位男士是一对舞伴，两位女士是一对舞伴，在伴，在“加催化剂加催化剂”的喊声中，他们交叉换位，转换的喊声中，他们交叉换位，转换为两对男女舞伴，在场记者随即发出了笑声。为两对男女舞伴，在场记者随即发出了笑声。为演示该理论，几位评委挑起了交换为演示该理论，几位评委挑起了交换舞伴的舞蹈舞伴的舞蹈 All life on Earth is ba

9、sed on these carbon compounds, but they can also be produced artificially through organic synthesis. The word metathesis means change-places. In metathesis reactions, double bonds are broken and made between carbon atoms in ways that cause atom groups to change places. This happens with the assistan

10、ce of special catalyst molecules. Metathesis can be compared to a dance in which the couples change partners. 基于金属有机化学的化学工艺(1) 钯催化的从乙烯出发合成乙醛(Wacker process)(2) Ziegler-Natta催化剂催化烯烃聚合;(3) Rh催化的烯烃氢化；(4) 美国孟山都公司Rh催化从MeOH和CO出发制备醋酸的工艺(5) 联合碳化公司的Rh催化的氢甲酰化生产醛的工艺;(6) 孟山都公司从合成气出发合成乙二醇的生产流程；(7) DuPont公司的尼龙-66

11、前体合成工艺； (8) BASF、Rohm & Haas公司的丙烯酸酯生产工艺;(9) 日本高沙香料公司的薄荷醇的不对称合成(10) 金属催化的不对称合成技术在药物合成工业的实际应用金属有机化学金属有机化合物的合成与表征CM (HM)键的形成CM (HM)键的断裂导向有机合成的金属有机化学金属中间体淬灭金属中间体生成金属中间体相互转化有机合成化学CC键的形成和断裂CX键的形成和断裂 第第 一一 章章 Introduction# 1760 Cradle of organometallic chemistryParis military pharmacy# 1827 Zeise (丹麦药剂

12、师)Zeises salt: KPtCl3C2H4First olefin complex （乙醇氯铂酸盐） (Whler 1828年合成尿素; 门及列夫1869年元素周期表)Liebig: 空想！1868年：Birnbaum证实Liebig是谁？是谁？ 蒸馏器的发明人蒸馏器的发明人 Justius Liebigs Annalen 创始人创始人 有机化学发展之父有机化学发展之父 # 1849 Frankland: 3 EtI + 3 ZnEt2Zn + EtZnI + ZnI2 Skill for the manipulation of air-sensitive compounds. He的

13、发现者：searching for radical The most successful failure! # 1890 L. Mond: Ni(CO)4: used in a commercial process for refining nickel. Dr Ludwig Mond (March 7, 1839 December 11, 1909), was a German-born chemist and industrialist who took British nationality.Mond discovered nickel carbonyl, a previously u

14、nknown compound, which could be easily decomposed to produce pure nickel from its ores through the Mond process:Nickel oxide is reacted with Syngas at 200 C to remove oxygen, leaving impure nickel. Impurities include iron and cobalt.NiO (s) + H2 (g) Ni (s) + H2O (g) 2. The impure nickel is reacted w

15、ith excess carbon monoxide at 50 - 60 C to form nickel carbonyl.Ni (s) + 4 CO (g) Ni(CO)4 (g) 3. The mixture of excess carbon monoxide and nickel carbonyl is heated to 220 - 250 C. On heating, tetracarbonyl nickel decomposes to give nickel:Ni(CO)4 (g) Ni (s) + 4 CO (g) # 1899 P. BarbierH3CH3COCH31.

16、CH3I/Mg2. H2OH3CH3COHCH3H3CBarbiers student: V. Grignard (starting from 1900-)(1912 Nobel prize)Victor GrignardFrench chemist in full Franois-Auguste-Victor Grignard born May 6, 1871, Cherbourg, France died Dec. 13, 1935, Lyon French chemist and corecipient, with Paul Sabatier, of the 1912 NobelPriz

17、e for Chemistry for his developmnet of the Grignard reaction. This work in organomagnesium compounds opened a broad area of organic synthesis. In 1898, while a student under Philippe Barbier at Lyon, Grignard began his prizewinning work with a study of the alkylzinc compounds developed earlier by Si

18、r Edward Frankland. It was Barbier who had Grignard repeat some experiments on the preparation of a tertiary alcohol from a mixture of methyl heptyl ketone, magnesium, and methyl iodide. Grignard hit upon the idea of treating the iodide with the magnesium first and carried out the reaction in ether.

19、 This first of the Grignard reagents was a complete success. Grignards doctoral dissertation (1901) described the preparation of alcohols, acids, and hydrocarbons by means of reactions of organomagnesium compounds. He became a professor of chemistry at Nancy (1910) and at Lyon (1919). At the time of

20、 his death some 6,000 papers reporting applications of the Grignard reaction had been published.“for his method of hydrogenating organic compounds in the presence of finely disintegrated metals whereby the progress of organic chemistry has been greatly advanced in recent years”Paul Sabatier W. Schle

21、nk From: 2 Li + R2Hg To: 2 RLi + HgWilhelm Schlenk: The Man Behind the Flask Angew. Chem. Int. Ed. 2001, 40, 331.1951年发现二茂铁: 合成 (P. L. Pauson, T. J. Kealyof Duquesene University)Nature 1951, 168, 1039. FeOrange crystalline: very stable1952: S. A. Miller et al. at British Oxygen Co. (already has this

22、 compound for three years)J. Chem. Soc. 1952, 632.1952: R. B. Woodward, G. Wilkinson (Harvard Univ.) E. O. Fischer (Univ. Munich)ferrocene structure based on physical measurementfell short of proofShortly after: X-ray (Penn. State College and Oxford Univ.)C & EN News 2001, Dec. 3, P. 37烯烃金属键理论：M

23、. J. S. Dewar Bull. Soc. Chim. Fr. 1951, 1 8 , C79. J. Chatt and L. A. Duncanson J. Chem. Soc., 1953, 2939. 用于说明 Zeises salt 的结构影响 Hoechst-Wacker process (石化工业的巨大变革）Chatt: Imperial Chemical Industries Ltd. (ICI is now a subsidiary of Dutch chemicals group Akzo Nobel)“找门路找门路”Directing effects in inor

24、ganic substitution reactionsPart I. A hypothesis to explain the trans-effect J. Chatt, L. A. Duncanson, L. M. Venanzi, J. Chem. Soc., 1955, 4456-4460.# 1953 G. Wittig (1979 Nobel Prize)# 1955 E. O. Fisher: (C6H6)2Cr: bis(benzene)chromium# 19531955 K. K. Ziegler (Max-Plank 煤炭研究所) 2Al, NiCH2CH3-H elim

25、ination 乙酰丙酮基锆阻止H 消除 Polyolefins: TiCl4/AlEt3 G. Natta (意大利 Milano 工大): visiting 丙烯聚合？ Catalyst: transition metal/AlR3 1963 Nobel Prize Ethylene + AlEt3?What is Ni?Ni is a transition metal.Here comes the story.# 1956 H. C. Brown: Hydroboration (1979 Nobel Prize) 在AlCl3存在下NaBH4还原有机化合物 油酸乙酯CH3(CH2)7CH

26、=CH(CH2)7COOEt: 2.4 equiv! (Subba Rao from India) (1912-2004)CHB# 1963 第一届金属有机国际会议(辛辛那提) JOrganometal. Chem. 创刊# 1964 E. O. Fisher (CO)5WC(OMe)Me First carbene complex# 1965 G. Wilkinson, R. S. Coffey (Ph3P)3RhCl (1973 Nobel Prize with Fisher) # 1973 E. O. Fisher Carbyne complex (1973 Nobel Prize) 1

27、976: for his (H. C. Brown) studies on the structure of boranes illuminating problems of chemical bonding 1981 Fort Collins (Chair: L. S. Hegedus)The 1st International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis13th OMCOS: GenevaOrganometallics at Lake Geneva -by H. Buten

28、schn Angew. Chem. Int. Ed. 2005, 44, 5556-5558.A true fireworks display of palladium-catalyzed reactions was then presented by this years winner of the OMCOS award, S. Ma (Shanghai), who lectured on transition-metal-catayzed reactions of allenes. The carbometalation of allenes either leads to p-ally

29、l complexes or to alkenyl metal compounds. A subsequent b-hydride elimination leads to new allenes. Ma also reported on multi-component reactions. A special bonus at the end of his impressive lecture was a rhodium-catalyzed synthesis of steroid 6 from bisallenes 5, which was carried out in 74% yield

30、 Eq. (2). If the central C(CO2Me)2 unit in 5 is replaced by NTs (Ts = toluene-4-sulfonyl), diazasteroid 7 forms in 57% yield.5 mol% RhCl(CO)(PPh3)2solvent, refluxMeOOCMeOOCCOOMeCOOMeHHHMeO2CMeO2C747514th: Nara, Japan, August 2-6, 200715th: UK16th: China 2011年7月24-28日，由国际纯粹与应用化学联合会（IUPAC）主办，中国科学院上海有机

31、化学研究所和华东师范大学共同承办的第十六届导向有机合成的金属有机化学国际研讨会（16th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS 16)在上海国际会议中心成功召开，麻生明院士和丁奎岭研究员共同担任大会主席 。 2010年化学诺贝尔奖得主Ei-ichi Negishi教授应邀做了题为Magical Power of d-Block Transition MetalsPd-Catalyzed Cross-Coupling and Zr-Ca

32、talyzed Asymmetric Carboalumination of Alkenes (ZACA)的大会报告。# 1983 R. G. Bergman, W. A. G. GrahamC-H ActivationNature 2007, 446, 391-393.Why is CH activation such big news?What stimulated chemists to work onC H activation?How are hydrocarbons converted intomore useful compounds?What exactly is meant

33、by activation?Are there any other methods foractivating CH bonds?When did CH activation reallytake off?Are there any enzymatic CH activation reactions?络络合合物物： 元素离子( 或 原 子) 和 配 位 体( 常是 含 有 孤 对 电 子 的 分 子 或 离子) 生 成的 络 合 离 子 或 中 性 络 合 分 子。 Fe(CN)64- H3NBF3配 位 化 合 物： 过 渡 元 素 络 合 物 (1) 中 心 离 子 (2) 配 位 体：配

34、 位 数( 2-12)一一、 轨轨 道道 杂杂 化化 及及 配配 位位 化化 合合 物物 的的 几几 何何 构构 型型 1、 氧 化 态 M X : X ( 配 体) 以 满 壳 层 离 开 时，金 属 所 保 留 的 电 荷 MClxM+1M NM0M CH3CHHHxM+1Fe(CO)5C = OFe0 2 2. . 过过 渡渡 金金 属属 原原 子子 的的 电电 子子 层层 结结 构构3d 4s4d 5s5d 6s d, s 轨 道 能 量 相 近， d/ s 跃 迁N i 3d84s2 d103 3、 金金 属属 离离 子子 的的 d d 电电 子子 数数、 配配 位位 数数 及及 几

35、几 何何 构构 型型(1) d10 Zn2+, N i0, Pd0, Pt0dspsp3sp3 杂 化， 正 四 面 体例 如： N i(C O )4( 2) d9 Cu2+dspdsp2ds p2 杂 化， 正 方 形例 如： Cu( NH3)42+(3) d8 Pd2+, N i2+dsp2 杂 化， 正 方 形(4) d7 d2sp3 杂 化， 正 八 面 体Co(CN )64-(5) d6 d2sp3 杂 化， 正 八 面 体(6) d5, d4 d2sp3 杂 化， 正 八 面 体Fe(CN )63- M n(CN )64-Cr(CN )64- M n(CN )63-(7) d2d4

36、sp3 杂 化， 正 十 二面 体二二、 1 18 8 电电 子子 规规 则则 (The 18 Valence Electron Rule ) Sidgwick, 1927 Thermodynamically stable transition-metal organometallics are formed when the sum of the metal d electrons plus the electrons conventionally regarded as being supplied by the ligands equals 18. 1 1、 金金 属属 离离 子子 的的

37、 价价 态态 Pd(PPh3)4 Pd(0) N i Cl2(PPh3)2 N i (2+)2 2、 配配 体体 的的 种种 类类 及及 电电 子子 数数 a. 单 电 子 配 体 Cp2ZrHZrCp2H b. 二 电 子 配 体CO2, CH2=CH2, CH CH , R3P, R3N ,pyri di ne, acet one, X-, H-, R-, Ph-, C=C-c. 三 电 子 配 体d. 四 电 子 配 体 (COD)CH3Mn(CO)5 Mn+1 6 (d6) CH3 2 5 CO 2x5 total 18 Mn: 3d54s2FeOCCOCOFe08 (d8)2x23

38、CO 2x3total18Fe: 3d64s2NiNi(0)d104 C=C4x218Cr Cr(0) d62 benzene 6x218Ni: 3d84s2Cr: 3d54s1Fe2+ d62-2x6FeRh+PF6-18Rh3+ d6C=C 23 4 6184d85s13d64s2-h3(h5)bridged MMMor h3(trihapto)or h4or h6Ru(CO)3(1,2,3,4-tetrahapto-1,3,5-cyclooctatriene) tricarbonylrutheniumFeCO(1,2,3-trihaptocycloheptatrienyl) pentah

39、aptocyclopentadienylcarbonylironTi(5-C5H5)2(1-C5H5)2TiFeOCR2PFeCOPR2cis-Fe2(5-C5H5)2(CO)2(-PR2)2例 外： f elements Class Number of valence electrons 18 VE rule I . 16 17 18 19 not obeyed II . 16 17 18 not exceeded III 18 obeyed 18 electrons Nucleophilic 18 electrons Electrophilic 配配 位位 场场 理理 论论 配 位 体 与 过 渡 金 属 中 心 间 的 作 用 看作 是 配 位 体 的“ 力 场” 和 中 心 离 子产 生 相 互 作 用。一一. . 晶晶 体体 场场 理理 论论 金 属 离 子5 个d 轨 道 在 配 位 体 影响 下 发 生 能 级 裂 分。4/9dxy dyz dxzdz2 dx2-y2dz2 dx2-y2dxy dyz dxzdx2-y2dx-ydz2dyz dxz四 面 体 场 八 面 体 场 正 方 形(1) (1) 紫紫 外外 可可 见见 光光 谱谱 d-d跃 迁(a) 配 位 体 的 影 响I-Br-Cl-CNS-F-OH-HCO2-C2O42-H2OSC