Organometallic Chemistry

Dr. Ashwini Wadegaonkar

Unit 5: Organometallic Chemistry

• Definition of Organometallic compounds and Organometallic

chemistry
• CO as a π-acid donor ligand
• Binary metal carbonyls
• Methods of synthesis –
(a) Direct reaction
(b) Reductive carbonylation
(c) Photolysis and thermolysis
• Molecular and electronic structures (18 electron rule) of metal
carbonyls
• Homogenous catalysis – Hydroformylation, (Oxo Process) and
Wacker Process.
Organometallic chemistry

• Organometallic (OM) chemistry is the study of compounds containing, and

reactions involving, metal-carbon bonds.

• Main group elements, transition metals as well as lanthanides and actinides

form bonds to carbon.
• They are used widely as reagent or catalysts in organic synthesis.
• They are getting emphasis due to potential applications in homogeneous
catalysts, as reagents in organic synthesis and as makers in molecular
biology.
https://www.slideshare.net/satyabratasendh/metal-carbonyls-
92974314
Organometallic compounds
• Organometallic compounds are chemical compounds which contain
at least one bond between a metallic element and a carbon atom
belonging to an organic molecule.

• Even metalloid elements such as silicon, tin, and boron are known
to form organometallic compounds which are used in some
industrial chemical reactions.
Properties of Organometallic Compounds
• The bond between the metal and the carbon atom is often highly covalent in nature.
• Most of the organometallic compounds exist in solid states, especially the compounds in
which the hydrocarbon groups are aromatic or have a ring structure.
• The compounds consisting of highly electropositive metals such as sodium or lithium are
very volatile and can undergo spontaneous combustion.
• In many cases, organometallic compounds are found to be toxic to humans (especially the
compounds that are volatile in nature).
• These compounds can act as reducing agents, especially the compounds formed by highly
electropositive metals.
• The properties of organometallic compounds differ amongst each other based on the
properties of the metals that constitute them.
Applications of Organometallic Compounds

• In some of the 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 of the 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.
Carbonyl complexes

• An analysis of Metal-CO bonding shows two types of bonding –

a) A sigma - σ bond formed by donation of an electron pair from the
carbon atom of CO into a vacant orbital on the metal centre
b) Two pi-bonds are formed by back donation of electrons form
filled metal dл orbitals into л2 orbitals of CO. this back bonding
leads to an increase in bond order of M-C bond and a decrease in
C-O bond order.
CO as a π-acid donor ligand

• π acid ligands are one which are capable of

accepting an appreciable amount of electron density
from the metal atom into empty or orbital of their
own are called as acid or acceptor ligands.

• This type of interaction increases the value of crystal

field splitting energy and thus are classified as
strong filed ligands.

• Example of pi acid ligands are CO, NO+ and CN-

• The electron pair located on carbon is more loosely bound and
it is available for donation to metal.
• CO has a pair of empty mutually perpendicular л*orbitals that
overlap with filled metal orbitals of л symmetry and help to
drain excess negative charge from the metal to the ligands.
• Because the ligands containing empty л*orbitals accept
electrons, they are Lewis acids and are called л acids.
• Metal to ligand electron donation is referred as back bonding.
• https://youtu.be/y9FZQBvgWPo
• Energetically σ bond is formed between metal
and ligand, a σ bond is formed by donation of an
electron pair from the carbon atom of CO into
vacant orbital on the metal (L M)

• Back bonding assumes greater relative

importance when metal has many electrons to
dissipate, thus low oxidation states are stabilized
by л acid ligands.

• σ and л bonding reinforce each other, this

mutual reinforcement is called as synergism.
Binary metal carbonyls

• Binary carbonyls are the simplest class of л acid

complexes.
• Most of them are available commercially.
• Table 5.1
Methods of synthesis

• Simple transition metal carbonyls are made by various methods, the

important ones are –

(a) Direct reaction

(b) Reductive carbonylation

(c) Photolysis and thermolysis

(a) Direct reaction

• First of all tetracarbonyl nickel [Ni(CO)4] and

pentacarbonyl iron [Fe(CO)5] were discovered in
1888.
• The synthesis of [Ni(CO)4] is inducstrially
important because the reaction is reversible and
this is the basis of the Mond’s process for
purification of metallic nickel.
250C Distill
• Ni + 4CO --> Ni(CO)4 Ni + 4CO
1 atm ∆ Pure
Impure
• The simplest metal carbonyls are the neutral binary Mx(CO)y
compounds, these may be mononulear (x=1) or polynuclear (x>1).
The majority of metal carbonyls are ow melting point solids that can
be sublimated in vacuo. A small number of the compounds are
volatile liquids.

• The other mononuclear metal carbonyls are prepared by direct

reaction of metal with gaseous CO at appropriate temperatures and
pressures.

• Example –

2000C 2000C
• Fe + 5 Co Fe (CO)5 , Mo + 6 CO Mo(CO)
100 atm 250 atm
(b) Reductive carbonylation

• Mononuclear and polynuclear metal caarbonyls are synthesized by

a process known as reductive carbonylation in which a transition
metal in a high oxidation state is reduced to zero oxidation state in
presence of CO gas.

• Often these reactions are performed at very high pressures in steel

bombs

• To reduce the possibility of an accident the bombs are usually

operated in explosion proof rooms, located on the top floor of a
chemistry building.
• Some typical metal carbonyls synthesis employing
reductive carbonylation are shown as –

AlCl3
• CrCl3 + Al + 6CO Cr(CO)9 + AlCl3
C6H6

• When halide is not present, CO can serve as the reducing agent

• Re2O7 + 17 CO Re2(CO)10 + 7CO2

1500C
• 2 CoCO3 +2 H2 +8 CO Co2(CO)8 + 2CO2 + 2H2O
250 atm
(c) Photolysis and thermolysis

• In addition to direct reaction and reductive carbonylation methods,

carbonyl compounds can also be synthesized by a route called
occurs photolysis. Photochemical bond cleavage occurs during
synthesis

• Eg. Sysnthesis of iron ennearcarbonyl.

hv
2 Fe(CO)5 Fe2(CO)9 + CO

hv
2Na[V(CO)6] + 2 HCl 2 V(CO)6 + 2 NaCl + H2
Molecular and electronic structures

• 5.5. book
18 electron rule of metal carbonyls
• The 18-electron rule is used primarily for predicting and
rationalizing formulae for stable metal complexes, especially
organometallic compounds.

• The rule is based on the fact that the valence shells of transition
metals consist of nine valence orbitals (one s orbital, three p orbitals
and five d orbitals), which collectively can accommodate 18
electrons as either bonding or nonbonding electron pairs.

• This means that, the combination of these nine atomic orbitals with
ligand orbitals creates nine molecular orbitals that are either metal-
ligand bonding or non-bonding.

• When a metal complex has 18 valence electrons, it has achieved the

same electron configuration as the noble gas in the period.
• The rule and its exceptions are similar to the application of the octet
rule to main group elements.
18 electron rule of metal carbonyls
• This rule applies primarily to organometallic compounds, and the 18 electrons
come from the 9 available orbitals in d orbital elements (1 s orbital, 3 p orbitals,
and 5 d orbitals).
• The rule is not helpful for complexes of metals that are not transition metals,
and interesting or useful transition metal complexes will violate the rule because
of the consequences deviating from the rule bears on reactivity.
• If the molecular transition metal complex has an 18 electron count, it is
called saturated.
• This means that additional ligands cannot bind to the transition metal because
there are no empty low-energy orbitals for incoming ligands to coordinate.
• If the molecule has less than 18 electrons, then it is called unsaturated and can
bind additional ligands.
18 electron rule of metal carbonyls

The transition metal complexes may be classified into

the following three types -
(i) The ones that do not obey the 18 valence electron
rule are of class I type
(ii) The ones that do not exceed the 18 valence
electron rule are of class II and
(iii) The ones that strictly follow the 18 valence
electron rule.
18 electron rule of metal carbonyls

Depending upon the interaction of the metal orbitals with

the ligand orbitals and also upon the nature of the ligand
position in spectrochemical series, the transition metal
organometallic compounds can form into any of the
three categories.
18 electron rule of metal carbonyls
To count electrons in a transition metal compound:

1. Determine the oxidation state of the transition metal and the

resulting d-electron count.
a) Identify if there are any overall charges on the molecular
complex.
b) Identify the charge of each ligand.
2. Determine the number of electrons from each ligand that are
donated to the metal center.
3. Add up the electron counts for the metal and for each ligand.

Typically for most compounds, the electron count should add up to 18

electrons. However, there are many exceptions to the 18 electron
rule, just like there are exceptions to the octet rule.
• Examples

• https://chem.libretexts.org/Bookshelves/Inorga
nic_Chemistry/Map%3A_Inorganic_Chemistry
_(Housecroft)/24%3A_Organometallic_chemist
ry%3A_d-block_elements/24.03%3A_The_18-
electron_Rule
Homogenous catalysis
• Hydroformylation (Oxo Process) and
• Wacker Process.
Hydroformylation (Oxo Process)

• Hydroformylation, popularly known as the "oxo" process, is a Co or

Rh catalyzed reaction of olefins with CO and H2 to produce the
value-added aldehydes.

• The reaction, discovered by Otto Roelen in 1938, soon assumed an

enormous proportion both in terms of the scope and scale of its
application in the global production of aldehydes.

• The metal hydride complexes namely, the rhodium based

HRh(CO)(PPh3)3 and the cobalt based HCo(CO)4 complexes,
catalyzed the hydroformylation reaction as shown below.
This chemical reaction entails the addition of a formyl group (CHO) and a
hydrogen atom to a carbon-carbon double bond. This process has
undergone continuous growth since its invention in 1938: Production
capacity reached 6.6×106 tons in 1995.

It is important because the resulting aldehydes are easily converted into

many secondary products.
• For example, the resulting aldehydes are
hydrogenated to alcohols that are converted to
plasticizers or detergents.

• Hydroformylation is also used in specialty

chemicals, relevant to the organic synthesis of
fragrances and natural products.

• The development of hydroformylation, which

originated within the German coal-based industry, is
considered one of the premier achievements of
20th-century industrial chemistry.
Wacker Process
• The Wacker oxidation was originally developed as the process of
producing acetaldehyde from ethylene using the PdCl2-
CuCl2 cocatalytic system. Molecular oxygen can be used as the
terminal oxidant.

• The reaction can be used to oxidize various terminal alkenes to give

the corresponding methyl ketones. DMF is used often as the solvent.

• Internal alkenes are usually unreactive, thus terminal alkenes can be

oxidized selectively when both are present in the same molecule.
• The cooperative catalytic cycle involves the oxidation of
the alkene by Pd(II), the oxidation of Pd(0) by Cu(II),
and the oxidation of Cu(I) by molecular oxygen.

• Similar cycle is used to manufacture acetone from

propylene if OH- is replaced by acetate, vinyl acetate can
be made.
Reaction Mechanism