1. Organometallics in Organic Synthesis
유기금속유기합성화학
Organometallics in Organic Synthesis
담당교수: 전철호 (과 410: )
References: Power Point with Handout
Organotransition Metal Chemistry –Fundamental Concepts and Applications –Wiley Interscience- (1986)
A. Yamamoto
2) Transition Metals in the Synthesis of Complex Organic Molecules
University Science Books (1994)
L. S. Hegedus
Homogeneous Catalysis –Understanding the Art-
Kluwar Academic Publishers (2005)
P. W. N. M. van Leeuwen

2. 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 s or a p bond. (‘coordination compounds’ such as Ti(OR)4 are not involved in organotransition metal compounds)

3. O,O’-bonded acetylacetonato ligand
Purely inorganic compounds such as carbides and cyanides are not classified
As organometallic compounds even though they contain metal-carbon bonds.
Metal carbonyls and hydrides are usually included in the field of organometallic
Chemistry because they show organic character in many cases.
N2-containing compounds are treated similarily.
Boron and Silicon are usually regarded as nonmetal, but organoboron and
Organosilicon compounds are regarded as organometallic compounds.

4. 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.

5. 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.

6. 1.2 Historical Background of Organometallic Chemistry
In 1827, Danish W. C. Zeise; Ann. Phys, 9, 632 (1827)
In 1849 E. Frankland; Ann., 71, 171 (1849)

7. In 1899, V. Grignard: Compt. Rend., 130, 1322 (1900)
In 1890, L. Mond; J. Chem. Soc., 57, 749 (1890)
B,p, 43oC, mp -25oC
Solvay Process: in nickel vessel, sada ash (Na2CO3)
from NaCl, CO2, ammonia
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

8. In 1925, F. Fischer and H. Tropsch
In 1938, O. Roelen
Siloxane Polymer insulator: G. E.
In 1940, E. G. Rochow
Direct Synthesis

9. In 1950s developments
In 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 (1953)
In 1951, Kealy and Pauson; Nature, 168, 1039 (1951),
Miller Fe(0) +cyclopentadiene; J. Chem. Soc. 632 (1952)

10. 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;

11. 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 1961, L. Vaska’s complex Ir(CO)(PPh3)2
J. Am. Chem. Soc. 83, 2784 (1961)
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

14. 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