유기금속유기합성화학 Organometallics in Organic Synthesis
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Transcript of 유기금속유기합성화학 Organometallics in Organic Synthesis
유기금속유기합성화학Organometallics in Organic Synthesis
담당교수 : 전철호 ( 과 410: 2123-2644)
References: Power Point with Handout1) Organotransition Metal Chemistry –Fundamental Concepts and
Applications –Wiley Interscience- (1986) A. Yamamoto2) Transition Metals in the Synthesis of Complex Organic Molecule
s University Science Books (1994) L. S. Hegedus3) Homogeneous Catalysis –Understanding the Art- Kluwar Academic Publishers (2005) P. W. N. M. van Leeuwen
Introduction
• Organotransition metal chemistry is concerned with compounds which have an organic group bonded to a transition metal through a direct metal-carbon bond, either a or a bond. (‘coordination compounds’ such as Ti(OR)4 are not involved in organotransition metal compounds)
HCO
PtO
OCH
OH3C
H3C
CH3
CH3
Py HCO
PtO
O
H3C
H3COH3C
CH3H
Py
O,O’-bonded acetylacetonato ligand
Purely inorganic compounds such as carbides and cyanides are not classifiedAs organometallic compounds even though they contain metal-carbon bonds.
Metal carbonyls and hydrides are usually included in the field of organometallicChemistry because they show organic character in many cases.
N2-containing compounds are treated similarily.
Boron and Silicon are usually regarded as nonmetal, but organoboron andOrganosilicon compounds are regarded as organometallic compounds.
• Inclusion of organophosphorus compounds is disputable: Chemical abstracts and the journal of Orgnometallic chemistry regarded as organometalloid compounds.
• Metal complexes having tertiary phosphine, PH3,or PF3 are often treated in organometallic chemistry.
Organotransition metal chemistry
• Transition metals may be strictly defined as those that have partly filled d shells as elements. It is more common to adopt a broader definition to include copper, silver, and gold as transition metals, since they have partly filled d shells in some of their oxidation states.
• The organozinc, cadmium, and mercury compounds are not treated since these compounds contain no partly filled d shells in their most common oxidation state of +2 and they are more appropriately discussed as organometallic compounds of non transition metals.
PtCl2 or PtCl4EtOH
KClPt
Cl
HClCl
CH2
CH2
-
K+ H2O.
1.2 Historical Background of Organometallic Chemistry
In 1827, Danish W. C. Zeise; Ann. Phys, 9, 632 (1827)
2 C2H5I + 2 Zn [ 2 C2H5ZnI]C2H5-Zn-C2H5 + ZnI2
In 1849 E. Frankland; Ann., 71, 171 (1849)
Ni + 4 CO Ni(CO)4
In 1890, L. Mond; J. Chem. Soc., 57, 749 (1890)
B,p, 43oC, mp -25oC
In 1899, V. Grignard: Compt. Rend., 130, 1322 (1900)
1912 nobel Prize winner
R-Mg-X
In 1917, W. Schlenk R-Li
In 1921, T. Midgeley and T. A. Boyd
PbEt4
Solvay Process: in nickel vessel, sada ash (Na2CO3) from NaCl, CO2, ammonia
In 1925, F. Fischer and H. Tropsch
CO + H2Co catalystor iron oxide
CH3(CH2)nOH, CH3(CH2)nCH=CH2CH3(CH2)nCH3, H2O µî
In 1938, O. Roelen
CO + H2 +Co2(CO)8 Catalyst
200-300 atm, 120-170oC
CHO
Siloxane Polymer insulator: G. E. In 1940, E. G. RochowDirect Synthesis
CH3Cl + SiCu, 300µµ
(CH3)2SiCl2, (CH3)3SiCl, CH3SiCl3 µî
In 1950s developmentsIn 1951, Orgel described back bonding of metal carbonyl M.J.S. Dewar explained metal-ethylene pi bonding Bull. Soc. Chim. Fr., 18, C17 (1951)
In 1953, J. Chatt and L. A. Duncanson extended these theories J. Chem. Soc. 2939 (1953)
In 1951, Kealy and Pauson; Nature, 168, 1039 (1951), Miller Fe(0) +cyclopentadiene; J. Chem. Soc. 632 (1952)
MgBr + FeCl22
Fe
¶ÇÂ
Fe++- -
FeH
H
dihydrofulvaleneferroceneÀÇ ±¸Á¶
In 1955, G. Wilkinson and E.O. Fischer described structure of Ferrocene. In 1973, they won the Nobel Prize.G. wilkinson, M. Rosenblum, M. C. Whiting, R. B. Woodward, J. Am. Chem.Soc.74, 2125 (1952); E. O. Fischer, W. Pfab. Z. Naturforsch., 7B, 377 (1952)
1953 Mark-Plank Institute: K Ziegler developed polyolefin Polymerization catalyst: diethylaluminum chloride and titanium tetrachloride.G. Natta developed regular structured polyalkene product. In 1963, they won the Nobel Prize
In 1956, H.C Brown: Hydroboration; J. Am. Chem. Soc. 78, 5694 (1956)
In 1957, J. L. Spier: Hydrosilylation;
In 1961 D. C. Hodgkin elucidated the structure of Coenzyme B12. Nature, 192, 937 (1961)
In 1976, R. B. Woodward synthesized this, collaborated with Eschenmoser.
In 1963, first issue of Journal of Organometallic Chemistry was published. In 1964, Synthesis of the first carbene-metal complex by E.O. Fischer; Angew. Chem. Int. Ed. Engl. 3, 580 (1964)
; Discovery of Olefin metathesis reaction by R. L. Banks
In 1965, Discovery of Wilkinson’s catalyst by G. Wilkinson
In 1961, L. Vaska’s complex Ir(CO)(PPh3)2
J. Am. Chem. Soc. 83, 2784 (1961)
In 1972, Monsanto Process: methanol + CO - acetic acid by Rh catalyst
In 1974, L-Dopa (Parkinson’s disease’ treatment) was produced.
In 1982, Organometallics was first published from American Chemical Society
In 1982, R. G. Bergman, W. D. Jones, Graham developed C-H bond activation