Organometallic

Compounds
Module 2
 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.

• It excludes carbides (CaC2) and cyanides (NaCN)

• It includes Wilkinson's catalyst [RhCl(PPh3)3]

• Organic molecule can be carbonyl, alkyl, alkene, aromatic, cyclic or heterocyclic.

• Metallic element can be metals or metalloids (B, Si, Ge, and As)

• The bond between the metal atom and the carbon belonging to the organic compound is
generally covalent in nature but can be ionic too.

• Metals with relatively high electropositivity (such as sodium and lithium) form these
compounds, a carbanionic nature is exhibited by the carbon which is bound to the central
metal atom.
Examples
 Hapticity
• Hapticity is the coordination of a ligand to a metal center via an
uninterrupted and contiguous series of atoms.
• The hapticity of a ligand is described with the Greek letter η ('eta') followed by
superscript indicating the number of ligand attached to the metal.
The ligand which can change its hapticity are called fluxonial lignand
 The 18-electron Rule
• The 18 Electron rule: It states that thermodynamically stable transition metal
compounds contain 18 valence electrons comprising of the metal d electrons
plus the electrons supplied by the metal bound ligands.
• The tendency of the central metal to achieve the noble gas configuration in its
valence shell
• The rule is based on the fact that the valence shells of transition metals consist of
nine valence orbitals (1 s orbital, 3 p orbitals and 5 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 is not helpful for complexes of non transitional metals.
 Electron counting
• Neutral atom method: Metal is taken as in zero oxidation state for counting
purpose
• Oxidation state method: We first arrive at the oxidation state of the metal by
considering the number of anionic ligands present and overall charge of the
complex
• Neutral atom method:
• Identify the group number of the metal centre.
• Identify the number of electrons contributed by the ligands.
• Identify the overall charge of the metal-ligand complex.
• At the presence of metal-metal bond, one electron is counted towards each
metal centre in a bond.
• Add up the group number of the metal centre and the e- count of the ligands,
then take into consider the overall charge of the complex to obtain the final
electron count.
 Electron counting
• Identify the group number of the metal centre.
• Identify the number of electrons contributed by the ligands.
• Identify the overall charge of the metal-ligand complex.
• At the presence of metal-metal bond, one electron is counted towards each
metal centre in a bond.
• Add up the group number of the metal centre and the e- count of the
ligands, then take into consider the overall charge of the complex to obtain
the final electron count.
 Ligand Covalent Charge

H 1 -1

Cl, Br, I 1 -1

OH, OR 1 -1

CN 1 -1

CH3, CR3 1 -1

NO (bent M-N-O) 1 -1

NO (linear M-N-O) 3 +1

CO, PR3 2 0

NH3, H2O 2 0
 Ligand Covalent Charge
CNR 2 0
=O, =S 2 -2
η3-C3H5 (π-allyl) 3 +1
≡CR (carbyne) 3 0
≡N 3 -3
en (Ethylenediamine) 4 0
bipy (Bipyridine) 4 0
butadiene 4 0
η5-
C5H5 (cyclopentadieny 5 -1
l)
η6-C6H6 (benzene) 6 0
η7-
C7H7 (cycloheptatrien 7 +1
yl)
 Examples
Complexes Covalent Method

•Fe gives 8e-

(η5-C5H5)2Fe •2 η5-C5H5 give 2×5e-
•Complex Charge is 0

•V gives 5e-
[V(CO)7]+ •7 CO give 7×2e-
•Complex Charge is +1 (-1e-)

•Re gives 7e-

•5 CO give 5×2e-
Re(CO)5(PF3)]+
•PF3 gives 2e-
•Complex Charge is +1 (-1e-)
• A few common examples of exceptions to 18 electron rules include:

• 16-electron complexes: The metal center is usually low-spin and is in

d8 configuration. These complexes adopt square planar structure,
such as Rh(I), Ni(II), Pd(II), and Pt(II) complexes. In a lot of catalytic
reactions, the organometallic catalysts convert back and forth
between 18 and 16 electron configurations, and thus completes a
catalytic cycle.

• Bulky ligands may hinder the completion of 18 electron rule.

• Complexes with ligands of strong π-donating characters often violate

18 electron rule. Examples of this kind of ligands include F-, O2-, RO-
and RN2-.
• The 18 electron rule is usually followed in metal complexes with strong field
ligands that are good σ donors and π acceptors (for example, CO ligands). The
energy difference (Δ0) between t2g and eg* orbitals is very large, and in this case
the three t2g orbitals become bonding and are always filled, while the two eg*
orbitals are strongly antibonding and are always empty.

• However, when Δ0 between t2g and eg* orbitals are small, for example, in the case
of first row transition metals with weaker field ligands, the antibonding character
of eg* orbitals weakens, and the complex can have up to 22 electrons.

• On the other hand, less than 18 electrons may be observed in complexes of 4th
and 5th row transition metals with high oxidation states. In this case, Δ0 is
relatively large due to increased repulsion between d orbitals of metals and the
ligands. The eg* orbitals are strongly antibonding and remains empty, while
t2g orbitals are non-bonding, and may be occupied by 0-6 electrons. [2]
 Classification of Transition metal
organometallic compounds
• Transition metal organometallic compounds mainly belong to any of
the three categories.
• Class I complexes for which the number of valence electrons do not
obey the 18 VE rule.
• Class II complexes for which the number of valence electrons do not
exceed 18.
• Class III complexes for which the valence electrons exactly obey the
18 VE rule.
In class I complexes, the Δo splitting is small and often applies to 3d metals and σ ligands
at lower end of the spectrochemical series. In this case the t2g orbital is nonbonding in
nature and may be occupied by 0−6 electrons. The eg* orbital is weakly antibonding and
may be occupied by 0−4 electrons. As a consequence, 12−22 valence electron count may
be obtained for this class of compounds. Owing to small Δtetr splitting energy, the
tetrahedral transition metal complexes also belongs to this class.

In class II complexes, the Δo splitting is relatively large and is applicable

to 4d and 5d transition metals having high oxidation state and for σ ligands in the
intermediate and upper range of the spectrochemical series. In this case, the t2g orbital is
essentially nonbonding in nature and can be filled by 0−6 electrons. The eg* orbital is
strongly antibonding and is not occupied at all. Consequently, the valence shell electron
count of these type of complexes would thus be 18 electrons or less.

In class III complexes, the Δo splitting is the largest and is applicable to good σ donor and
π acceptor ligands like CO, PF3, olefins and arenes located at the upper end of the
spectrochemical series. The t2gorbital becomes bonding owing to interactions with ligand
orbitals and should be occupied by 6 electrons. The eg* orbital is strongly antibonding
and therefore remains unoccupied.
 Zeise’s salt
• Danish pharmacist William C. Zeise in 1827 prepared
first synthetic organometallic compound, K[PtCl3(C2H4)]
• When platinum tetra chloride reacts with ethanol an adduct is
formed, which react with KCl gives Zeise’s salt. The following two
method for preparation of Zeise’s salt are shown below.

130°C
 Structure of zeies salt
The structure contains an ethylene molecule (H2C=CH2) attached through both carbon
atoms to the central platinum (Pt) atom. The platinum atom also is bonded to
three chlorine (Cl) atoms. The potassium ion, K+, is present to balance the charge.

• The greater the sigma donation to the

metal, the greater the pi-backbonding.
• The greater the electron density back-
donated into the pi* orbital on the alkene,
the greater the reduction in the C=C bond
order i.e the hybridization of the alkene
carbon changes from sp2 to sp3 as back-
donation increases.
• As a consequence, the C –C bond length
in Zeise’s salt increases from free
C2H4 molecule ( 1.34 Å) to
coordinated C2H4 molecule (1.4 -1.47 Å).
 Chromium hexacarbonyl Cr(CO)6
Cr(CO)6 is zerovalent, homoleptic complex
The complex is octahedral with Cr–C and C–O distances of 1.91 Å and 1.14 Å, respectively.
 Ligand-transfer reactions

A unique double ligand-transfer reaction was reported with using chromium

trichloride and chromium hexacarbonyl. In reactions, potassium perrhenate(VII) is
reduced and carbonylated by the chromium reagents and undergoes Cp ligand-
transfer to afford CpRh(CO)3 complex derivatives.
 Dimanganese decacarbonyl Mn2(CO)10.
• Mn2(CO)10 has no bridging CO ligands: it can be described as containing two
axially-linked (CO)5Mn- subunits.
• There are two kinds of CO ligands; there is one CO linked to each Mn atom that is
coaxial with the Mn-Mn bond and there are four “equatorial” carbonyls bonded
to each Mn atom that are nearly perpendicular to the Mn-Mn bond (Mn’-Mn-
CO(equatorial) angles range from 84.61 to 89.16 degrees).
• Mn subunits are positioned at a distance of 290.38(6) pm.
• The axial carbonyl distance of (181.1 pm) is 4.5 pm shorter than the average
equatorial manganese-carbonyl distance of 185.6 pm.
 Synthesis
• Mn2(CO)10 is a golden yellow solid which was first synthesized by
carbonylation of manganese iodide with carbon monoxide using magnesium
as a reducing agent under a pressure of 100−300 psi at room temperature.
• A more efficient preparation entails reduction of manganese acetate with
sodium benzophenone ketyl under 200 atmospheres of carbon monoxide.
 Ligand-transfer reactions

Ligand substitution reactions that do not disrupt the Mn-Mn bonding is done
by using strongly sigma donating L-type ligands that can outcompete CO
without participating in redox reactivity. This requirement usually
necessitates phosphines with substitution occurring at the axial position
according to the reactions below
 Cisplatin
• Cisplatin was discovered in 1845 by Michel Peyrone and the structure
was deduced by Alfred Werner in 1893. Licensed for medical use in
1979.
• Cisplatin is a chemotherapy medication used to treat a number of
cancers.
• Cisplatin is a heavy metal complexes containing a central atom of
platinum surrounded by two chloride atoms and two ammonia
molecules in the cis position.
• Cisplatin is a white lyophilized powder soluble in water or saline.
• Cisplatin is administered intravenously as short-term infusion in
normal saline.
 Synthesis
• Synthesis of cisplatin start from potassium tetrachloroplatinate. The conversion of K2PtCl4 to K2PtI4.
• Reaction with ammonia forms PtI2(NH3)2 which is isolated as a yellow compound.
• When silver nitrate in water is added insoluble silver iodide precipitates and
[Pt(OH2)2(NH3)2](NO3)2 remains in solution.
• Addition of potassium chloride will form the final product which precipitates.
• In the triiodo intermediate the addition of the second ammonia ligand is governed by the trans effect.
 Mechanism of Cisplatin
• One chloride ligand is slowly displaced by water resulting in the formation of
[PtCl (H2O)(NH3)2].
• Due to which can bind to bases easily especially to guanine [PtCl (guanine-DNA)
(NH3)2]+.
• On displacement of another Chlorine molecule by water the cisplatin molecule
can bind to another guanine in the same DNA molecule forming a cross link
between the two strands.
• After complete binding of the Cisplatin the DNA molecule will bend at a 30 deg.
Angle. This leads to DNA damage.
• The damaged DNA elicits DNA repair mechanism which leads to apoptosis.
• Common side effects include bone marrow suppression, hearing problems,
kidney damage, and vomiting. Other serious side effects include numbness,
trouble walking, allergic reactions, electrolyte problems, and heart disease.
Mechanism of Cisplatin
 Calcium Disodium Ethylenediamine Tetraacetic Acid
(CaNa2EDTA)
• Metal toxicity may occur due to essential metal overload or exposure to heavy
metals from various sources.
• Chelation therapy is the preferred medical treatment for reducing the toxic
effects of metals.
• Chelating agents are capable of binding to toxic metal ions to form complex
structures which are easily excreted from the body removing them from
intracellular or extracellular spaces.
• a derivative of ethylenediamine tetraacetic acid (EDTA) used for the treatment of
lead poisoning in children since 1950.
• The metals that have higher affinity for chelating agent than the Ca2+. The
successful use of CaNa2EDTA in the treatment of lead poisoning is due to the
capacity of lead to displace calcium from the chelate.
• The Pb-EDTA complex has high stability constant thus CaNa2EDTA was found to
chelate lead from the body fluids, excreting PbNa2EDTA leaving Ca behind.
• EDTA is FDA-approved for the treatment of lead poisoning in adults and
children. EDTA has the ability to bind lead tightly and is more effective than
other common chelators.
• EDTA is also used in a diagnostic test to assess levels of lead present within
patients.
• While not approved by the FDA, EDTA has the ability to bind other heavy
metals within the body, including zinc, cadmium, mercury, and iron.
• CaNa2EDTA is poorly absorbed in the gastrointestinal tract (<5%) thus can
be administered intravenously.
• EDTA is distributed throughout the entire extracellular compartment.
Within the blood, the molecule stays within the plasma. It has an ionic
form preventing it from entering into cells.
• After IV administration, calcium EDTA largely goes unmetabolized and is
excreted in its administered form through the kidneys. Similarly, the
chelate-metal complexes will be quickly excreted in the urine. The half-life
is around 20 to 60 minutes. The kidneys can filter out the drug.
 Side effects
• There are multiple adverse effects related to the use of EDTA. The most
commonly recognized adverse effect is renal toxicity. The toxic effects can
manifest as acute tubular necrosis, renal failure, anuria, and proteinuria.

• Calcium EDTA has a strong affinity for zinc, which can lead to a zinc deficiency.

• Other side effects include fever, nausea, vomiting, chills, fatigue, hypotension,
arrhythmias, tremors, headache, bone marrow depression, anemia, and
hypercalcemia. Pain at the injection site is a common adverse drug reaction of
intramuscular administration.
 Wilkinson's catalyst
Chloridotris(triphenylphosphine)rhodium(I)
• square planar geometry.

Synthesis
• Wilkinson's catalyst is usually obtained by treating rhodium(III) chloride
hydrate with an excess of triphenylphosphine in refluxing ethanol.
• In the synthesis, three equivalents of triphenylphosphine become ligands in the
product, while the fourth reduces rhodium(III) to rhodium(I).

RhCl3(H2O)3 + 4 PPh3 → RhCl(PPh3)3 + OPPh3 + 2 HCl + 2 H2O

Catalytic Hydrogenation of Alkenes
 Mechanism of Catalysis for the Hydrogenation of
Alkenes
• Initially, a complex is formed from the dissociation of 1 or 2
triphenylphosphine ligands.
• Now, the oxidative addition of molecular hydrogen (H2) to the metal core of
Wilkinson’s catalyst (rhodium) occurs forming 18-electron complex.
• The third step of the mechanism involves the formation of a pi complex with
the alkene.
• The hydrogen is inserted into the complex via migratory insertion which could
proceed through intramolecular hydride transfer or through olefin insertion.
• Finally, reductive elimination occurs at the pi complex to regenerate the
catalyst and afford the required alkene product.
Wilkinson Decarbonylation
 Ziegler-Natta Polymerization
• German chemist named Karl Ziegler in the year 1950
• The method was extended to other olefins by an Italian chemist known as Giulio
Natta
• Ziegler and Natta were awarded the Nobel Prize in 1963.
• Ziegler-Natta catalysts today usually contain many mixtures of halides belonging
to transition metals like titanium, vanadium, chromium, zirconium and organic
derivatives of non-transition metals especially that of alkyl aluminium
compounds.
• This reaction is of high industrial importance for the production of olefins like
polyethylene.
• Polymerisation usually takes place by the insertion of monomers where the
transition metal ions are attached to the end of the growing chain.
• The incoming monomers are simultaneously coordinated at vacant orbital sites,
and there is a formation of long polymer chains.
Ziegler-Natta Polymerization
 Heck reaction (Mizoroki–Heck reaction)
• The reaction of an unsaturated halide (or triflate) with an alkene in the
presence of a base and a palladium catalyst to form a substituted alkene.
• It is named after Tsutomu Mizoroki and Richard F. Heck.
• Heck was awarded the 2010 Nobel Prize in Chemistry, for the discovery
and development of this reaction.
• This reaction was the first example of a carbon-carbon bond-forming
reaction that followed a Pd(0)/Pd(II) catalytic cycle.
• The Heck reaction is a way to substitute alkenes.
Mechanism of Heck reaction
 Suzuki coupling reaction
• The Suzuki reaction is an cross-coupling reaction, where the coupling partners
are a boronic acid and an organohalide and the catalyst is a palladium(0)
complex.
• It was first published in 1979 by Akira Suzuki, and he shared the 2010 Nobel
Prize in Chemistry with Richard F. Heck and Ei-ichi Negishi for their
contribution to the discovery and development of palladium-catalyzed cross-
couplings in organic synthesis.
• This reaction is also known as the Suzuki–Miyaura reaction or simply as the
Suzuki coupling.
• It is widely used to synthesize polyolefins, styrenes, and substituted biphenyls.
• The general scheme for the Suzuki reaction is shown below, where a carbon-
carbon single bond is formed by coupling an organoboron species (R1-BY2)
with a halide (R2-X) using a palladium catalyst and a base.
•
 Mechanism of the Suzuki Coupling
• The mechanism of the Suzuki reaction is best viewed from the perspective of the
palladium catalyst 1.
• The first step is the oxidative addition of palladium to the halide 2 to form
the organopalladium species 3.
• Reaction (metathesis) with base gives intermediate 4, which via transmetalation with
the boron-ate complex 6 (produced by reaction of the boronic acid 5 with base) forms
the organopalladium species 8.
• Reductive elimination of the desired product 9 restores the original palladium
catalyst 1 which completes the catalytic cycle.
• The Suzuki coupling takes place in the presence of a base and for a long time the role
of the base was not fully understood.
• Duc and coworkers investigated the role of the base in the reaction mechanism for
the Suzuki coupling and they found that the base has three roles: Formation of the
palladium complex [ArPd(OR)L2], formation of the trialkyl borate and the acceleration
of the reductive elimination step by reaction of the alkoxide with the palladium
complex.
Mechanism of the Suzuki Coupling
 Oxidative addition
• In most cases the oxidative addition is the rate determining step of the catalytic
cycle.
• During this step, the palladium catalyst is oxidized from palladium(0) to
palladium(II).
• The palladium catalyst 1 is coupled with the alkyl halide 2 to yield an
organopalladium complex 3.
• The oxidative addition step breaks the carbon-halogen bond where the palladium
is now bound to both the halogen and the R group.
 Transmetalation
• Transmetalation is an organometallic reaction
where ligands are transferred from one species
to another.
• In the case of the Suzuki coupling the ligands are
transferred from the organoboron species 6 to
the palladium(II) complex 4 where the base that
was added in the prior step is exchanged with
the R1 substituent on the organoboron species to
give the new palladium(II) complex 8.
• The organoboron compounds do not undergo
transmetalation in the absence of base and it is
therefore widely believed that the role of the
base is to activate the organoboron compound
as well as facilitate the formation of R2-Pdll-OtBu
from R2-Pdll-X.
 Reductive elimination
• The final step is the reductive elimination step where the palladium(II) complex 8
eliminates the product 9 and regenerates the palladium(0) catalyst(1). Using
deuterium labelling, Ridgway et al. have shown the reductive elimination
proceeds with retention of stereochemistry.

• The ligand plays an important role in the Suzuki reaction. Typically, the phosphine
ligand is used in the Suzuki reaction. Phosphine ligand increases the electron
density at the metal centre of the complex and therefore helps in the oxidative
addition step.
 Application
• The coupling of 3-pyridylborane and 1-bromo-3-
(methylsulfonyl)benzene that formed an intermediate that was used
in the synthesis of a potential central nervous system agent. The
coupling reaction to form the intermediate produced (278 kilograms)
in a 92.5% yield.