Applications Of Organometallic Compounds

Submitted To: Royea Rehman

Submitted By: Usama talib

Reg.No: Bschem01181069

Department: Chemistry

Semester: BS 7th (Organic Chemistry)

Subject:[ Heterocyclic And

Organometallic Chemistry]

The University Of Lahore New Campus (Department of

chemistry BS 7th)
 Introduction To Organometallic Compounds

• Organometallic compound, any member of a class of substances containing at least

one metal-to-carbon bond in which the carbon is part of an organic group.
• Organometallic compounds constitute a very large group of substances that have played a
major role in the development of the science of chemistry.
• They are used to a large extent as catalysts (substances that increase the rate of reactions
without themselves being consumed) and as intermediates in the laboratory and in industry.
• The class includes such compounds as ferrocene, a remarkably stable compound in which
an iron atom is sandwiched between two hydrocarbon rings.

• Organometallic compounds are typically discussed in terms of the metal as either main-
group compounds or transition metal compounds.
• The main-group metals of organometallic compounds are typically considered to be those
of the S-block (groups 1 and 2) and the heavier elements of the p-block (groups 13–15) in
the periodic table of elements.
• The transition metals include those elements in the d- and f-blocks (groups 3–12).
• The physical and chemical properties of organometallic compounds vary greatly. Most are
solids, particularly those whose hydrocarbon groups are ring-shaped or aromatic, but some
are liquids, and some are gases.
• Their heat and oxidation stability vary widely. Some are very stable, but a number of
compounds of electropositive elements such as lithium, sodium, and aluminum are
spontaneously flammable. Many organometallic compounds are highly toxic, especially
those that are volatile.
• The properties of the organometallic compounds depend in large measure on the type of
carbon-metal bonds involved. Some are ordinary covalent bonds, in which pairs
of electrons are shared between atoms.
• Others are multicenter covalent bonds, in which the bonding involves more than two atoms.
• A third type are ionic bonds, in which the bonding electron pair is donated by only one atom.
In donor-acceptor bonds, the metal atom is connected to hydrocarbons with multiple bonds
between carbon atoms.
• Where metal atoms form covalent bonds with carbon atoms, the electrons are usually shared
unequally. As a result, the bond is polarized—one end is more negative than the other.

• The extent of polarization depends on the strength with which the metal atom binds
electrons. Organometallic compounds range in polar power from methyl potassium, in
which the bond is almost like certain ionic bonds, to lead, which bonds with carbon with
very little polarization.
Applications Of Organometallic Compounds

• Because of bond polarity, many organometallic compounds have reactivities that have
made them important in chemical synthesis.
• The organomagnesium halides (Grignard reagents), for example, are used widely
in synthetic organic chemistry, as are organolithium and organoboron compounds.
• Alkylaluminium compounds are also employed in organic synthesis. Used
with titanium salts, they are important catalysts in the polymerization of unsaturated
hydrocarbons, such as ethylene and propylene.
• The mechanism of action of the titanium-aluminum alkyl catalysts probably involves
interaction between the titanium atoms and the double bonds of the hydrocarbons.
• Organometallic compounds containing lead, tin, and mercury are all commercially
significant.
• A large number of organotin compounds, for example, are used
as pharmaceuticals, pesticides, stabilizers for polyvinyl chloride, and fire retardants.
• Methylmercury has caused severe pollution problems as a result of its toxicity. This fact
has led to stringent controls on the discharge of mercury from chemical plants into rivers,
lakes, and oceans.
• Carbon monoxide reacts readily with many transition-metal atoms to form metal
carbonyls, themselves a class of organometallics.

• One of the earliest to be discovered was tetracarbonyl nickel, a volatile nickel compound
that became the basis of a process for purifying nickel. Metal carbonyls are employed as
catalysts in many reactions in the petrochemical industry.

• A compound is regarded as organometallic if it contains at least one metal-carbon (M―C)

bond where the carbon is part of an organic group.
• Typically, an organic group contains carbon-hydrogen (C―H) bonds; for example, the
simple methyl group, CH3, and larger homologs such as the ethyl group, C2H5, which
attach to a metal atom through only one carbon atom. (Simple alkyl groups such as these
are often abbreviated by the symbol R.)
• More elaborate organic groups include the cyclopentadienyl group, C5H5, in which all five
carbon atoms can form bonds with the metal atom.
• The term metallic is interpreted broadly in this context; thus, when organic groups are
attached to the metalloids such as boron (B), silicon (Si), germanium (Ge),
and arsenic (As), the resulting compounds are considered to be organometallic along with
those containing true metals such as lithium (Li), magnesium (Mg), aluminum (Al),
and iron (Fe).
• The “metal” in an organometallic compound can include most elements, with the
exception of nitrogen (N) and phosphorus (P) in group 15 and all the elements in groups
16 (the oxygen group), 17 (halogens), and 18 (noble gases).
• One example of an organometallic compound is trimethyl boron, B(CH3)3, which contains
three B―C bonds.
• Another is ferrocene, Fe(C5H5)2, which has a more elaborate structure with the iron atom
sandwiched between two C5H5 rings.

• Some compounds with metal-carbon bonds are not regarded as organometallic, because
the constituent carbon atom is not part of an organic group; two examples are
metal carbides—such as Fe3C, a hard solid that is a component of cast iron—and
metal cyanide compounds—such as the deep-blue paint pigment Prussian blue,
KFe2(CN)6.

• In some commercial chemical reactions, organometallic compounds are used as

homogeneous catalysts.
• These compounds are used as stoichiometric reagents in both industrial and research-
oriented chemical reactions.
• These compounds are also used in the manufacture of some semiconductors, which
require the use of compounds such as trimethylgallium, trimethylaluminum,
trimethylindium, and trimethyl antimony.
• They are also used in the production of light emitting diodes (or LEDs).
• These compounds are employed in bulk hydrogenation processes such as the production
of margarine.
• These compounds are used as catalysts and reagents during the synthesis of some organic
compounds.
• The complexes formed from organometallic compounds are useful in the facilitation of
the synthesis of many organic compounds.
• The application of organometallic complexes in homogeneous catalysis.
• Alkene isomerization.
• Alkene and the arene hydrogenations.
• Transfer hydrogenation.
• One of the most important exploits of the organometallic chemistry is its application in the
area of homogeneous catalysis.
• The field has now expanded its territory to accommodate in equal measures many large-
scale industrial processes as well as numerous small scale reactions of the day-to-day
organic synthesis.
• A few representative examples of organometallic catalysis are outlined below.
 Alkene Isomerization

• Alkene isomerization is a transformation that involve a shift of a double bond to an

adjacent position followed by 1,3−migration of a H atom. The isomerization reaction is
transition metal catalyzed.

• The alkene isomerization reaction may proceed by two pathways,

• one through a η1−alkyl intermediate and
• the other through η3−allyl intermediate. In the η1−alkyl pathway, an alkene first binds to
a metal at a vacant site next to M−H bond and then subsequently undergoing an insertion
into the M−H bond thus creating back the vacant site.
• The resultant species then undergoes a H atom transfer from the alkyl moiety to give the
isomerized olefin along with the regeneration of the M−H species.

• The η3−allyl mechanism requires the presence of two vacant sites.

• This mechanism goes through a η3−allyl intermediate formed by a C−H activation at the
allylic position of the olefin formed after binding to the metal and alongside leads to the
formation of a M−H bond. Subsequent H transfer from the metal back to the η3−allyl moiety
leads to the alkene isomerized product.

Alkene Hydrogenation

• The transition metal catalyzed alkene hydrogenation reactions are of significant industrial
and academic interest.
• These reactions involve the H2 addition on a C=C bond of olefins to give alkenes. The
alkene hydrogenation may proceed by three different pathways namely the
• oxidative addition
• heterolytic activation and
• the homolytic activation of the H2 molecule.
• The oxidative addition pathway is commonly observed for the Wilkinson’s catalyst
(PPh3)3RhCl and is the most studied among all of the three pathways that exist. The
catalytic cycle initiates with the oxidative addition of H2 followed by alkene coordination.
• The resultant species subsequently get converted to the hydrogenated product.
• The second pathway proceeds by the heterolytic activation of the H2 molecule and requires
the presence of a base like NEt3, which facilitates the heterolytic cleavage by abstracting a
proton from the H2 molecule and leaving behind a hydride H− ion that participates in the
hydrogenation reaction.
• This type of mechanism is usually followed by the (PPh3)3RuCl2 type of complexes.

• Homolytic cleavage of H2 is the third pathway for the alkene hydrogenation. It is the rarest
of all the three methods and proceeds mainly in a binuclear pathway.
• Paramagnetic cobalt based Co(CN)53− type catalysts carry out alkene hydrogenation by this
pathway via the formation of the HCo(CN)53−species.
 Arene hydrogenations

• Examples of homogeneous catalysts for arene hydrogenation are rare though it is routinely
achieved using catalysts like Rh/C under the heterogeneous conditions.
• A representative example of a homogeneous catalyst of this class is
(η3−allyl)Co[P(OMe)3]3 that carry out the deuteration of benzene to give the all-cis-
C6H6D6 compound.
 Transfer hydrogenation

• This is a new kind of a hydrogenation reaction in which the source of the hydrogen is not the
H2molecule but an easily oxidizable substrate like isopropyl alcohol.
• The method is particularly useful for the reduction of ketones and imines but not very
effective for the olefins.

Me2CHOH+RCH=CH2⟶Me2C=O+RCH2CH3