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Faculty of Science/Chemistry department Organometallic chemistry - 3 Stage – 6 semester

Introduction
Organometallic chemistry is a branch of chemistry which includes the study of
chemical compounds containing bonds between carbon and metal atoms.
Organometallic chemistry involves the creation of compounds with C-M bonds with C-δ-
M+δ, as compared to that of an organic compound, which contains nonpolar C-C bonds.
The partial negative charge on such carbon of an organometallic compound is the origin
of its majority of applications, as it invokes the tendency to make a nucleophilic attack in
that carbon and, in turn, facilitates a wide variety of organic reactions.
Compounds with at least one bond between metal and carbon of an organic group are
known as organometallic compounds. Organometallic compounds, with their metal–
carbon bonds, are placed at the interface between classical organic and inorganic
chemistry in dealing with the interaction between inorganic metal species and organic
molecules.
Hence, compounds like Ti(OC4H9)4, Ca[N(CH3)2]2 and Fe(SC5H11)3 are not
organometallic compounds, but C6H5Ti(OC4H9)3 is an organometallic compound.
Cyanides such as NaCN and carbides such as CaC2 are not organometallic compounds.
We count them as inorganic compounds. While carbonyl compounds such as Ni(CO)4 are
counted as organometallic compounds.
Organometallic compounds have played a critical role in catalysis and organic synthesis,
often leading to more efficient use of reagents, higher yields of products, and less use of
energy. They have also been used as precursors in the preparation of nanomaterials and
microelectronic materials. Species containing M-C bonds have been found in biology as
well. The vitamin B12 coenzyme contains a Co-C bond.
Living systems contain a variety of organometallic compounds, prominent examples
being hemoglobin and chlorophyll.

S.Y: 2023-2024 Lecturer: Mr. Twana Mohammed

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Faculty of Science/Chemistry department Organometallic chemistry - 3 Stage – 6 semester

Historical Background
 French chemist Louis Claude Cadet de Gassicourt isolated the first organometallic
compound, tetramethyldiarsine or cacodyl, in 1757 by accident. He was
experimenting with invisible inks by combining arsenic containing cobalt ore with
potassium acetate. Arsenic itself is not a true metal, rather it is considered a metalloid,
and nonetheless it is still considered an organometallic compound.

 The first olefin complex synthesized in (1827) by Zeise, who obtained yellow needle
like crystals after refluxing a mixture of PtCl4 and PtCl2 in ethanol, followed by
addition of KCl solution. Zeise’s salt was the first compound identified as containing
an organic molecule attached to a metal using the pi electrons of the organic
molecule. It is an ionic compound of formula K[Pt(C2H4)Cl3].H2O [Potassium
trichloro(ethene)platinate(II)], the structure of the anion, as shown bellow; is based
on a square plane, with three chloro ligands occupying corners of the square and the
ethylene occupying the fourth corner, but perpendicular to the plane.

Anion of Zeise’s Salt

 1852 Frankland prepares the important alkylmercury halides.

S.Y: 2023-2024 Lecturer: Mr. Twana Mohammed

 rd th
Faculty of Science/Chemistry department Organometallic chemistry - 3 Stage – 6 semester

 In (1859) W. Hallwachs and A. Schafarik generate alkylaluminum iodides

 In (1863) C. Friedel and J. M. Crafts prepare organochlorosilanes:

 The first organometallic compound containing the carbonyl ligand, [PtCl2(CO)2] was
discovered by P. Schützenberger in (1868).
 In (1890), Mond reported the preparation of the first binary metal carbonyl
compound, Ni(CO)4, a compound that became commercially useful for the
purification of nickel.
 Reactions between magnesium and alkyl halides performed by Barbier in (1898) and
subsequently by Grignard led to the synthesis of alkyl magnesium complexes now
known as Grignard reagents, which used extensively in organic synthesis.
 In (1909) W. J. Pope: prepared [(CH3)3PtI], the first σ- organotransition-metal
compound.
 In 1951, in an attempt to synthesize fulvalene from cyclopentadienyl bromide, Kealy
and Pauson reacted the Grignard reagent cyclo- (C5H5)MgBr with FeCl3. This
reaction did not yield fulvalene but an orange solid having the formula (C5H5)2Fe,
ferrocene. For each of the cyclopentadienyl rings, all five of the C atoms are
equidistant from the metal ion, so that the two ring systems are parallel to each other
just like the slices of bread in a sandwich, with the metal stuck in between them.

S.Y: 2023-2024 Lecturer: Mr. Twana Mohammed

 rd th
Faculty of Science/Chemistry department Organometallic chemistry - 3 Stage – 6 semester

Nature and types of Metal-Carbon Bonding

Essentially, the five types of bonds listed below are observed between metal and carbon
in organometallic compounds. Many organometallic compounds have more than one type
of bond in them.
1. Metal–carbon ionic bonds
2. Metal–carbon covalent bonds
3. Metal–carbon three-centre two-electron bridge bonds
4. Metal–carbon π-bonds
5. Metal–carbon multiple bonds
Primarily, the electronegativity of the metal involved in the organometallic compounds
decides the percentage of ionic character in the metal–carbon bonds. The elements with
their positions farther from carbon in the periodic table form essentially ionic bonds.
Whereas the elements relatively near to carbon in the periodic table give metal–carbon
bonds with less ionic character. In the case of organometallic oligomers, if an electron-
deficient metal is involved, metal–carbon three-centre two-electron bridge bonds similar
to that of diborane are observed. Metal–carbon π -bonds are observed in the
organometallic compounds that contain the organic group with high π-acidity (the ability
to donate π-electrons). Organic compounds with one or more π-bonds can also donate
the π-electron density to form manifold bonds, as in Zeise’s salt.

S.Y: 2023-2024 Lecturer: Mr. Twana Mohammed