Organometallics in Organic Synthesis

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?????????? Organometallics in Organic Synthesis

• ???? ??? (? 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

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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)

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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.
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• 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.

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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.

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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)
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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
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In 1925, F. Fischer and H. Tropsch
In 1938, O. Roelen
Siloxane Polymer insulator G. E. In 1940, E. G.
Rochow Direct Synthesis
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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)
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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
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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. Vaskas 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 Wilkinsons
catalyst by G. Wilkinson
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In 1972, Monsanto Process methanol
CO -? acetic acid by Rh catalyst
In 1974, L-Dopa (Parkinsons 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
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