金属有机化学.ppt
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[Pt(CO)Cl2]2, first metal carbony(羰基) complex.
• D. I. Mendeleev uses organometallic compounds as test cases for his periodic table. Example:
Know: predicted found Si(C2H5)4 Eka-Si(C2H5)4
• 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).
• 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
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 ห้องสมุดไป่ตู้rsenic(砷) was used.
d = 0.96 d = 0.99
(C. Winkler, 1887)
Sn(C2H5)4 bp: 160℃ bp: 163.5 ℃
• 1890 L. Mond: Ni(CO)4, first binary(二元的) metal carbonyl, used in a commercial(商业的) process for refining nickel. Mond is the founder of the English company ICI (Imperial Chemical Industries) as well as a renowned collector and patron(恩主) of the arts.
• 1859 W. Hallwachs and A. Schafarik generate alkylaluminum iodides:
• 2Al + 3RI R2AlI + RAlI2 • 1863 C. Friedel and J. M. Crafts prepare
Organochlorosilane:
• 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.
X ZnI2 + 2C2H5
(C2H5)2Zn (a pyrophoric燃烧性的 liquid) ＋ C2H5ZnI(a solid) + ZnI2 Frankland possesses admirable skill in the manipulation(操作) of air sensitive compounds. As a protective atmosphere he uses hydrogen gas!
• 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).
3C2H5I + 3Zn
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.
• 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
• 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.
• D. I. Mendeleev uses organometallic compounds as test cases for his periodic table. Example:
Know: predicted found Si(C2H5)4 Eka-Si(C2H5)4
• 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).
• 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
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 ห้องสมุดไป่ตู้rsenic(砷) was used.
d = 0.96 d = 0.99
(C. Winkler, 1887)
Sn(C2H5)4 bp: 160℃ bp: 163.5 ℃
• 1890 L. Mond: Ni(CO)4, first binary(二元的) metal carbonyl, used in a commercial(商业的) process for refining nickel. Mond is the founder of the English company ICI (Imperial Chemical Industries) as well as a renowned collector and patron(恩主) of the arts.
• 1859 W. Hallwachs and A. Schafarik generate alkylaluminum iodides:
• 2Al + 3RI R2AlI + RAlI2 • 1863 C. Friedel and J. M. Crafts prepare
Organochlorosilane:
• 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.
X ZnI2 + 2C2H5
(C2H5)2Zn (a pyrophoric燃烧性的 liquid) ＋ C2H5ZnI(a solid) + ZnI2 Frankland possesses admirable skill in the manipulation(操作) of air sensitive compounds. As a protective atmosphere he uses hydrogen gas!
• 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).
3C2H5I + 3Zn
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.
• 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
• 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.