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