Organometallics in Organic Synthesis 유기금속유기합성화학 Organometallics in Organic Synthesis 담당교수: 전철호 (과 410: 2123-2644) 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

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)

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.

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.

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)

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

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

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. 2939 (1953) In 1951, Kealy and Pauson; Nature, 168, 1039 (1951), Miller Fe(0) +cyclopentadiene; J. Chem. Soc. 632 (1952)

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 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

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