Module-2:

Metal Complexes and

Organometallics

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 Contents…..(6 hours)

Inorganic complexes - structure, bonding and application;

Organometallics – introduction, stability, structure and applications

of metal carbonyls, ferrocene and Grignard reagent;

Metals in biology: haemoglobin and chlorophyll- structure and

property).

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 Inorganic Complexes: Structure, Bonding and Applications
❖ Double Salt: Double Salts and Coordination Compounds
Ferric alum
(NH4)2SO4.Fe2(SO)4.24H2O
In water: NH4+, SO42-, Fe3+

❖Co-ordination Compounds

3Cl– Fe(CN)2 + 4KCN Fe(CN)2.4KCN

(counterion)

4K+ + [Fe(CN)6]4-
ligand
(coordination sphere) M

N forms a coordinate covalent bond

to the metal
Ligands
▪ Molecule or ion having a lone electron pair that can be used to form a bond to a
metal ion (Lewis base).
▪ coordinate covalent bond: metal-ligand bond
▪ monodentate : one bond to metal ion
▪ bidentate : two bond to metal ion
▪ polydentate : more than two bonds to a metal ion possible

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Chelating Agents
• Bind to metal ions removing them
• Important biomolecules like heme
from solution.
and chlorophyll are porphyrins
• Phosphates are used to tie up
Ca2+ and Mg2+ in hard water to
prevent them from interfering with
detergents.
Werner Coordination Theory
Werner's Theory: Alfred Werner, Swiss chemist put forward a theory to explain the
formation of complex compounds.

Limitations:
1. Bonding within coordination sphere.
2. Square planar (or) Tetrahedral
Lewis Acid Base Theory - Gilbert N. Lewis, 1920s

❖ Lewis Acid/Base reactions: Base: electron pair donor; Acid: electron pair
acceptor
❖ Ligands: Lewis bases ; Metals: Lewis acids ; Coordinate covalent bonds
❖ Metal Complexes - Formation of a complex was described as an acid - base
reaction according to Lewis

Sidgwick’s Rule

❖ Sidgwick’s Effective atomic number (EAN) rule is based on the octet

theory of Lewis and this is the first attempt to account for the bonding in
complexes.
Valence Bond Theory (Linus Pauling, 1931)
Valence bond theory predicts that the bonding in a metal complex arises from
overlap of filled ligand orbitals and vacant metal orbitals.

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Tetrahedral Geometry
• Tetrahedral copper complex [CuCl4]2-

3d 4s 4p
Cu ground
state 3d94s2

Cu2+

4 e– pairs by Cl– ions

• One unpaired electron - paramagnetic and attracted by magnets

Square Planar Geometry
• Square planar nickel complex
[Ni(CN)4]2-
3d 4s 4p
Ni
(3d84s2)

Ni2+

[Ni(CN)4]2-

dsp2
• All paired electrons – diamagnetic - weakly repelled by magnets
Octahedral sp3d2 Geometry
Gives [CoF6]3– four unpaired electrons, which makes it paramagnetic and is called a high-spin
complex.
Ground state Co= (3d74s2)
Octahedral d2sp3 Geometry

[Fe(CN)6]3- Fe: (3d64s2)

3d 4s 4p

Fe+3

[Fe(CN)6]3-

CN– Strong ligand d2sp3

Bonding in Coordination Compounds
❖ Many of the properties of metal complexes are dictated by their electronic structures.

Crystal field theory (CFT)

❖ Electronic structure can be explained by an ionic model that attributes formal charges on to the metals
and ligands. This forms basis of crystal field theory (CFT), which is considered as the core concept in
inorganic chemistry.
❖ Consider bonding in a complex to be an electrostatic attraction between a positively charged nucleus
and the electrons of the ligands.
▪ Electrons on metal atom repel electrons on ligands.
▪ Focus particularly on the d-electrons on the metal ion.

❖ Ligand field theory (LFT) and the molecular orbital theory (MO) are considered sophisticated models as
compared to CFT. LFT explains complexes, wherein, the interactions are covalent.
Orbital occupancy for high- and low-spin complexes of d4 through d7 metal ions

high low spin:

high low spin: spin: strong-
spin: strong- weak- field ligand
weak- field ligand field
field ligand
ligand

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[Co(NH3)6]3+ > [Co(NH3)6]2+

[Co(NH3)6]3+ = 23,000 cm-1 (3d)

[Rh(NH3)6]3+ = 34,000 cm-1 (4d)

[Ir(NH3)6]3+ = 41,000 cm-1 (5d)

Spectrochemical Series
▪ For a given ligand, the color depends on the oxidation
state of the metal ion.

I- < Cl- < F- < OH- < H2O < SCN- < NH3 < en < NO2- < CN- < CO

WEAKER FIELD STRONGER FIELD

❖ Complexes of cobalt (III)
show the shift in color due
SMALLER Δ LARGER Δ
to the ligand.
❖ (a) CN–, (b) NO2–, (c) phen,
LONGER λ SHORTER λ (d) en, (e) NH3, (f) gly, (g)
H2O, (h) ox2–, (i) CO3 2–

• For a given metal ion, the color depends on the ligand.

Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
Spectrochemical series (strength of ligand interaction)
Effect of ligand on splitting energy

Increasing Δ
Cl- < F- < H2O < NH3 < en < NO2- < CN-

Increasing Δ

Low spin – color variations shown with increasing CFSE (Cr3+ = 24-3-18 = d3)
Applications of Coordination Compounds

❖Coordination compounds are of great importance.

❖Play many important functions in the area of analytical chemistry,
metallurgy, biological systems, industry and medicine.
• Catalysis
• Extraction of metal ions
• Analytical chemistry (development of numerous analytical
methods)
• Hardness estimation -
• Biological importance
• Medicinal application
• Industrial application
Extraction / Purification of metal

⮚ Extraction
❖ processes of metals, like those of silver and gold, make use of complex formation.

❖ These noble metals are extracted from their ore by the formation of cyanide complexes -
dicyanoargentite(I) - [Ag(CN)2]– and dicyanoaurate (I) - [Au(CN)2]– in the presence of oxygen
and water, from which the metallic forms can be separated by the addition of zinc.
▪ Ag2S + 4NaCN  2 Na[Ag(CN)2] + Na2S
▪ 2 Na[Ag(CN)2] + Zn  Na2[Zn(CN)4] + 2Ag↓

❖ Purification of metals can be achieved through formation and subsequent decomposition of

their coordination compounds. For example, impure nickel is converted to [Ni(CO)4], which is
decomposed to yield pure nickel.
Analytical chemistry
❖ In the qualitative methods of analysis, complex formation is of immense importance in the
identification and separation of most inorganic ions.

❖ Familiar colour reactions given by metal ions with a number of ligands (especially chelating
ligands), as a result of formation of coordination entities, form the basis for their detection and
estimation by classical and instrumental methods of analysis.
Examples of such reagents include EDTA, DMG (dimethylglyoxime), α–nitroso, β–
naphthol, cupron, etc.

❖ Since Cu is more stable then Cd. Therefore, on passing H2S only CdS is precipitated. Thus
Cd2+ ion easily detected in the presence of Cu2+ ions.
• Cu2+ + 4CN-  [Cu(CN)4]2-
• Cd2+ + 4CN-  [Cd(CN)4]2-
❖ Presence of Co and Fe can be detected by the formation of blue and blood red color
thiocyanate complexes respectively
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Detection of Complex formation
❖ Formation of Precipitate
Ni2+ + 2 HDMG [Ni(DMG)2] + 2H+

❖ Ni2+ and Pd2+ form insoluble colored precipitates with dimethyglyoxime

Biological Importance
❖ Pigment responsible for photosynthesis,
chlorophyll, is a coordination compound of
magnesium.
❖ Haemoglobin, the red pigment of blood
which acts as oxygen carrier is a
coordination compound of iron.
❖ Vitamin B12, cyanocobalamine, the anti-
pernicious anaemia factor, is a coordination
compound of cobalt.
❖ Other compounds of biological importance
with coordinated metal ions are the
enzymes like, carboxypeptidase A and
carbonic anhydrase (catalysts of biological Heme B: Heme B is a porphyrin (four linked pyrrole rings)
systems) that readily binds iron, as shown. This is an example of a
biomolecule that contains non-protein ligands for a
❖ Metalloprotein with the metal ion cofactor
transition metal.
have many diverse functions including
transport, storage, and signal transduction.
Medicinal Application
❖ To treat problems caused by the presence of
metals in toxic proportions in plant/animal systems,
chelate therapy is used.
• Excess of copper and iron are removed by the
chelating ligands D–penicillamine and
desferrioxime B via the formation of coordination
compounds.

❖ EDTA is used in the treatment of lead poisoning.

❖ Coordination compound of platinum effectively

inhibit the growth of tumours. cisplatin - cis
[PtCl2(NH3)2], and related compounds.
Chelation therapy
❖ D-penicillamine - Used in the treatment for
poisoning by heavy metals, including Wilson's
disease (build-up of copper in the body).
❖ Naturally occurring compounds such as
desferrioxamine B, belong to a group of
compounds called siderophores and are used
by bacteria to assist in the uptake of iron, can
also be used to remove unwanted iron by
chelation therapy.

▪ First World War - poisonous gases used in

the war was b-chlorovinyldichloroarsine
(Lewisite).
▪ Reacts with the SH groups of various
important enzymes British Anti-Lewisite
(BAL), 2,3-dimercaptopropanol. forms
stronger complex with arsenic – acts as an
antidote.
Industrial applications
• Coordination compounds are used as catalysts for many industrial
processes. Examples rhodium complex, [(Ph3P)3RhCl], a
Wilkinson catalyst - hydrogenation of alkenes.
• Articles can be electroplated with silver and gold much more
smoothly and evenly from solutions of the complexes, [Ag(CN)2]–
and [Au(CN)2]– than from a solution of simple metal ions.
• In black and white photography, the developed film is fixed by
washing with hypo solution which dissolves the non decomposed
AgBr to form a complex ion, [Ag(S2O3)2]3– .
• Prussian blue – Mixture of hexacyanoFe(II) and Fe(III) -
Fe4[Fe(CN)6]3 inks, blueprinting, cosmetics, paints (commercial
coloring agents)
▪ History of Prussian blue:
The first modern, artificially manufactured colour was Prussian blue. It was
made by the colormaker Diesbach of Berlin in about 1704. Diesbach
accidentally formed the blue pigment when experimenting with the oxidation
of iron. The pigment was available to artists by 1724 and was extremely
popular throughout the three centuries since its discovery.
Hardness of water

❖ Hardness of water is estimated by

titration with the sodium salt of EDTA.
❖ During titration, the calcium and
magnesium ions in hard water form the
stable complexes, Calcium EDTA and
Magnesium EDTA.
❖ Hardness of water is estimated by
simple titration with Na2EDTA.
❖ The selective estimation of these ions
can be done due to difference in the
stability constants of calcium and
magnesium complexes.
Representative Metal Complexes in Catalysis

• Zeise’s Salt : K[Pt(C2H4)Cl3]

• Magnus Green Salt : [Pt(NH3)4][PtCl4]
• Edman’s Salt : K[Co(NH3)2(NO2)4
• Reinecke’s Salt : NH4[Cr(NH3)2(NCS)4]
• Vaska’s Complex : [Ir(CO)(PPh3)2Cl]
• Wilkinson’s Catalyst : [Rh(PPh3)3Cl]
Organometallics – Introduction, stability, structure and
applications of metal carbonyls, ferrocene and Grignard
reagent

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What are Organometallics?
❖ An area which bridges organic and inorganic chemistry.
❖ A branch of coordination chemistry where the complex has one or more
metal-carbon bonds.
C always is more electronegative compared to M.
❖ The leading journals of the field define an "organometallic" compound as one in which there is a
bonding interaction (ionic or covalent, localized or delocalized) between one or more carbon atoms of
an organic group or molecule and a main group, transition, lanthanide, or actinide metal atom (or
atoms)
❖ Following longstanding tradition, organic derivatives of metalloids such as boron (B), silicon (Si),
germanium (Ge), arsenic (As), tellurium (Te) are also included in this definition.
Zeise’s Salt- The first transition metal ❖ Discovery 1827
organometallic compound: ❖ Structure ~ 150 years later

First σ-bonded Organometallic Compound- Diethyl Zinc:

3 C2H5I + 3 Zn → (C2H5)2Zn + C2H5ZnI + ZnI2
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First organometallics in homogeneous catalysis- The Hydroformylation (1938)

First Industrial plant-

hydroformylation

detergents
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Why are organometallics important?
❖ Are we dealing with ‘a’ special element?
❑ What is special about carbon?
• Forms bonds with other carbon atoms (C-C)
readily and they are strong (catenation)
• Forms strong multiple bonds (C=C)
• Forms very strong bonds with another special
element H!!
• Cyclic “C=C-C” fragments would be extra
stable - AROMATIC
❑ C and its electronic configuration!
1s2 2s2 2p2
❑ Why is this special ?
• To form a full shell, it would require 4 covalent bonds
• Gap between the 2s and 2p is just right!
• 1s2 2s1 2px12py12pz1
• When 4 equivalent covalent bonds are formed, no extra electrons / no vacant
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orbitals
Organic vs Organometallic reactivity
Organic chemistry Organometallic chemistry

▪ C is the negative end of the M-C bond

("umpolung")
▪ C-C/C-H bonds are covalent ▪ Reactivity dominated by nucleophilic
▪ Cδ+-Xδ- : polar (partly ionic) attack on metal atom and electrophilic
▪ Reactivity dominated by nucleophilic attack on carbon Atom
attack at carbon atom ▪ Associative and dissociative
▪ SN2 and SN1 like reactivity substitution at M 32
Some Important Ligand Nomenclature
“eta-x” was originally developed to indicate how many carbons of a π-system were

ηx coordinated to a metal center. Hapticity is another word used to describe the bonding
mode of a ligand to a metal center. An η5-cyclopentadienyl ligand, for example, has all
five carbons of the ring bonding to the transition metal center.
• ηx values for carbon ligands where the x value is odd usually indicate anionic carbon ligands
(e.g., η5-Cp, η1-CH3, η1-allyl or η3-allyl, η1-CH=CH2)
• The # of electrons donated (ionic method of electron counting) by the ligand is usually
equal to x + 1
• Even ηx values usually indicate neutral carbon π-system ligands (e.g., η6-C6H6, η2-
CH2=CH2, η4-butadiene, η4-cyclooctadiene)
• Number of electrons donated by the ligand in the even (neutral) case is usually just equal to x.

η5-Cp η3-Cp η3-allyl η1-allyl 33

µx “mu-x” is the nomenclature used to indicate the presence of a bridging ligand
between two or more metal centers. The x refers to the number of metal centers
being bridged by the ligand. Usually, most authors omit x = 2 and just use μ to
indicate that the ligand is bridging the simplest case of two metals.

❖ bridging ligands are usually placed next to the metals in question, then followed by the
other ligands (note that rules 1 & 2 take precedence): Co2(μ-CO)2(CO)6, Rh2(μ-Cl)2(CO)4,
Cp2Fe2(μ-CO)2(CO)2

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❖Organometallic compounds are classified into three classes.
• (i) Sigma (σ) bonded organometallic compounds: In these complexes, the metal atom and
carbon atom of the ligand are joined together with a sigma bond,
For Example:
• (a) Grignard reagents, R–Mg–X where R is an alkyl or aryl group, and X is a halogen.
• (b) Zinc compounds of the formula R2Zn such as (C2H5)2Zn
• Other similar compounds are (CH3)4Sn, (C2H5)4Pb, Al2(CH3)6, Al2(C2H5)6, Pb(CH3)4 etc.
Al2(CH3)6 is a dimeric compound and has a structure similar to diborane, (B2H6). It is an
electron deficient compound, and two methyl groups act as bridges between two aluminium
atoms.

(ii) Pi (π) bonded organometallic compounds:

These are the compounds of metals with alkenes,
alkynes, benzene and other ring compounds. In
these complexes, the metal and ligand form a
bond that involves the π-electrons of the ligand.
Three common examples are Zeise’s salt,
ferrocene and dibenzene chromium. These are
shown below.
 (iii) Sigma and π-bonded organometallic compounds

• Metal carbonyl compounds formed between metal and carbon monoxide,

belong to this class. These compounds possess both σ-and π-bonding.
Generally, oxidation state of metal atoms in these compounds is zero.
Carbonyls may be mononuclear, bridged or polynuclear.
Stability of Organometallic Compounds
❖ In general terms, the stability of an organometallic compound may refer to either its
thermal stability, or resistance to chemical attack (by air and moisture). Obviously,
these different types of stabilities would depend both on thermodynamic as well as
kinetic factors.

The organometallic compounds are generally hydrolysed via nucleophilic

attack by water, which is facilitated by:
(1) the presence of empty low-lying orbitals on the metal
(2) the polarity of metal-carbon bonds. Rate of hydrolysis is dependent on M-C
bond polarity – greater the polarity, faster will be the rate

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Thermal Stability
The thermodynamic stability of a compound relative to its constituent elements would
obviously depend upon the standard free energies of formation, ΔG°f values for
organometallic compounds, one has to rely on the known standard enthalpies of
formation, ΔH°f, making due allowance for plausible estimates for the contributions of
ths entropy terms TΔS, in the well-known relationship:

ΔG = ΔH ─TΔS
For example, let us for the purpose of simplicity consider that tetramethyllead
decomposes into lead, decomposes into lead, methane and ethane only, i.e.,

Pb(CH3)4 (g) → Pb(s) + 2CH4(g) + C2H4(g)

ΔH°f (kj/mol) +137 0 2×(-73) +52

The standard enthalpy change ΔHm for this reaction would be given by the difference
between the standard enthalpies of formation, ΔHf, for the products and reactants, i.e.,
ΔHm = ─146+52─137 = ─231 kj mol─1
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Factors influencing the stability/ reactivity of Organometallics
❖ The thermodynamic stability of metal-alkene complexes is strongly affected by the nature of
the alkene (and metal):
• 1) Electron-withdrawing groups on the alkene generally increase the strength of the
metal-alkene bonding, while electron-donating groups generally decrease the stability.
• 2) In cases where cis-trans isomerism is possible, the more stable complex is almost always
formed by the cis-alkene (steric factors).
• 3) Presence of β-hydrogen in the alkyl chains attached to the metal
▪ The main driving force for β-hydride elimination is the
formation of a stronger M-H bond (almost always stronger
than M-alkyl) and the generation of an alkene ligand that
reduces the unsaturation of the metal complex. The
reverse reaction, however, also can occur and is called a
migratory insertion.
▪ In order to prepare stable M-alkyl complexes one,
therefore, often needs to stay away from alkyls with β-
hydrogens (or avoid metals with empty coordination
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sites).
4. Metal complexes of ring-strained cycloalkenes (e.g., cyclopropene) display higher than
expected stability. The ring strain raised the energy of the cycloalkene ring system making it a
better donor to the metal center (better orbital energy matching). See the next section on
cyclobutadiene for a particularly remarkable example.
Cyclic conjugated π-systems are aromatic if the number of π-electrons equals 4n + 2 (where n
= an integer). Cyclobutadiene is an anti-aromatic since it has 4 π-electrons. The anti-
aromaticity combined with the ring strain makes this simple molecule too unstable to exist as a
free organic compound.
The high stability of a cyclobutadiene coordinated to a metal arises from the mixing of the 4 π
electrons on the cyclobutadiene with one of the metal d orbitals that has 2 e- and the right
symmetry to mix in and form a 6 π electron aromatic system!

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5. Chelating dienes show the expected stabilization from the chelate effect. The
most common examples are norbornadiene and cyclooctadiene shown below.
Note that these can still be easily substituted off the metal by stronger
coordinating ligands such as phosphines.

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 The 18-electron Rule or Effective atomic number (EAN)
❖ The 18e rule is a way to help us decide whether a given d-block transition metal organometallic
complex is likely to be stable. Not all the organic formulas we can write down correspond to
stable species. Recall: Second row elements (B, C, N, O, F) have 4 valence orbitals (1s + 3p) so
they can accommodate up to 8 valence electrons--the octet rule.
▪ For example, CH5 requires a 5-valent carbon and is therefore not stable. Stable compounds,
such as CH4, have the noble gas octet, and so carbon can be thought of as following an 8e rule.
▪ The 18e rule, which applies to many low-valent transition metal complexes, follows a similar line
of reasoning. The metal now has one s, and three p orbitals, as before, but now also five d
orbitals. We need 18e to fill all nine orbitals; some come from the metal, the rest from the ligands.
Therefore, we can expect that the low-lying MOs can accommodate up to 18 valence electrons--
The 18-Electron Rule.

❖ The rule states that “thermodynamically

stable transition metal organometallic
compounds are formed when the sum of the metal d electrons and the
electrons conventionally considered as being supplied by the surrounding
ligands equals 18”
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Counting electrons for metal complex
To count the electrons of a metal complex, one must:
a) note any overall charge on the metal complex
b) know the charges of the ligands bound to the metal center (ionic ligand method)
c) know the number of electrons being donated to the metal center from each ligand (ionic
ligand method)
Similarly for a transition metal complex, the electron count is the sum of the metal valence
electrons + the ligand centered electrons.
❖ Covalent Model: # e = # metal electrons (zero valent) + # ligand electrons - complex charge
Metal: The number of metal electrons equals its column number (i.e., Ti = 4e, Cr = 6e, Ni =
10e)
Ligands: In general L donates 2 electrons, X donates 1 electron.

❖ Ionic Model: # e = # metal electrons (dn) + # ligand electrons

Metal: Determined based on the number of valence electrons for a metal at the oxidation state
present in the complex
Ligands: In general and L and X are both 2 e donors.
❖ Complexes with 18 e- counts are referred to as saturated. 43
❖ Complexes with counts lower than 18e- are called unsaturated.
Electron Counting ❖ Step 2: Determine the d electron count.
Recall: subtract the metal's oxidation state from
❖ Step 1: Determine the oxidation state of the its group #.
metal. To do this, balance the ligand charges
with an equal opposite charge on the metal. This
is the metal's formal oxidation state. ❖ Step 3: Determine the
• To determine ligand charges, create an ionic electron count of the
model by assigning each M-L electron pair to the complex by adding the #
more electronegative atom (L). This should result of electrons donated by
in stable ligand species or ones known as each ligand to the metal's
reaction intermediates in solution. d electron count.

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Example 1
Please note that we are using the Ionic Method of electron-counting. 95% of
inorganic/organometallic chemists use the ionic method. The ionic method
assigns formal charges to the metal and ligands in order to keep the ligands
with an even # of electrons and (usually) a filled valence shell. Synthetically,
the ionic method generally makes more sense and the one that we will use in
this course.

1) There is no overall charge on the complex

2) There is one anionic ligand (CH3−, methyl group)
3) Since there is no overall charge on the complex (it Now we can do our electron counting:
is neutral), and since we have one anionic ligand Re(+1) d6
present, the Re metal atom must have a +1 charge to 2 PR3 4e-
compensate for the one negatively charged ligand. 2 CO 4e-
The +1 charge on the metal is also its oxidation state. CH3− 2e-
So the Re is the in the +1 oxidation state. We denote CH2=CH2 2e-
I
this in two different ways: Re(+1), Re(I), or Re .
Total: 18e- 45
HMn(CO)5
Mn(+1) d6 6e-
5 CO 10e-
H− 2e-
Total: 18e-

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Common Reactions of Organometallic Complexes

▪ Oxidative Addition
▪ Reductive Elimination
▪ Migratory Insertion
▪ Transmetallation
▪ β-Hydride Elimination

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❖ Oxidative Addition

A reaction in which (usually) a neutral ligand adds to a metal center and in doing so oxidizes
the metal, typically by 2e-. The transferring of the two electrons from the metal to the incoming
ligand breaks a bond in that ligand forming two new anionic ligands. At least one of these new
anionic ligands ends up bonded to the metal center.

WARNING: d0 metals can NOT do oxidative additions!! So always electron count the starting
and final metal complexes to check out the overall electron-count, metal oxidation state and d-
electron count! 48
❖Reductive Elimination
A reductive elimination reaction is the reverse of an oxidative addition. It is a reaction in which
two cisoidal anionic ligands on a metal center couple together. Each anionic ligand pushes
one electron back onto the metal center (in the case of a monometallic complex) to reduce it by
2e-. The coupled anionic ligands then usually fall off the metal center as a neutral molecule.

Since electron-rich metal complexes favor oxidative addition, the reverse is true for reductive
elimination. Since reductive elimination involves pushing electrons back onto the metal center
from two anionic ligands that are usually more electronegative than the metal center, it is best if
the metal center is electron deficient. This can be accomplished by having electron-withdrawing
ligands (e.g., CO), cationic charge(s), and/or coordinative unsaturation (sub-18e- counts). 49
❖ Migratory Insertion
▪ A migratory insertion reaction is when a cisoidal anionic and neutral ligand on a metal
complex couple together to generate a new coordinated anionic ligand. This new anionic
ligand is composed of the original neutral and anionic ligands now bonded to one another.
▪ General Features:
1) No change in formal oxidation state
(exception: alkylidenes)
2) The two groups that react must be cisoidal to
one another
3) A vacant coordination site is generated by
the migratory insertion. Therefore, a vacant site
is required for the back elimination reaction
(e.g., β-hydride elimination). A trapping ligand is
often needed to coordinate to the empty site
formed from a migratory insertion in order to
stop the back elimination reaction.
4) Migratory insertions are usually favored on
more electron-deficient metal centers.
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❖ Transmetallatio
n
▪ Definition: the transferof an organic group from one metal center to another. The process
involves no formal change in oxidation state for either metal.

▪ Transmetalation is often a reversible process,

with the equilibrium favoring the more ionic M-X
bond. Subsequent reactivity of one LnM-R
species can drive the equilibrium in one
direction. This is often exploited in cross-
coupling reactions, where a transmetalated
intermediate undergoes a reductive elimination
to generate a new organic product. Subsequent
oxidative additions generates a new substrate
for transmetalation
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❖ β-Hydride Elimination
▪ A significant decomposition pathway for metal alkyls is β-hydride elimination which converts a
metal alkyl into a hydrido metal alkene complex.

▪ β-hydride elimination can occur when:

o cis to the alkyl group there exists is a site of coordinative
unsaturation on the metal which corresponds to a site of
electronic unsaturation (empty metal orbital).
o The M-C-C-H unit can take up a coplanar conformation
which brings the β-hydrogen in close enough proximity to
the metal to form an agostic interaction.
o The metal is electrophilic resulting in an agostic
interaction that is primarily electron donative in nature
(i.e. σ-donation>>π-backbonding). 52
 Metal-Carbonyls

As one goes from a terminal CO-

bonding mode to μ2-bridging and
finally μ3-bridging, there is a relatively
dramatic drop in the CO stretching
frequency seen in the IR.

❖ Standard Bonding Modes

2e- neutral donor 2e- neutral donor 3e- neutral donor

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Three types (two of which are important) of CO-Metal bonding interactions

❖Formation of σ-bond:
▪ The overlapping of empty hybrid orbital on metal atom with the filled hybrid orbital on carbon
atom of carbon monoxide molecule through lone pair electrons results into the formation of a
M←CO σ-bond.
❖Formation of π-bond by back donation:
▪ This bond is formed because of overlapping of filled dπ orbitals or hybrid dpπ orbitals of metal
54
atom with antibonding pi orbitals on CO molecule.
Structure of Ni(CO)4

55
Ligand Donation Effects
The ability of the ligands on a metal to donate electron density to the metal center certainly has
considerable effect on the absolute amount of electron density on that metal. This, in turn, naturally
effects the νCO IR stretching frequencies in metal carbonyl complexes. Ligands that are trans to a
carbonyl can have a particularly large effect on the ability of the CO ligand to effectively π-
backbond to the metal. For example, 2 trans π-backbonding ligands will partially compete for the
same d-orbital electron density, weakening each others net M-L π-backbonding.

When the trans ligand is a σ-donating ligand, this can increase the M-CO bond strength (more
M=C=O character) by allowing unimpeded metal to CO π-backbonding. Pyridine and amines are
not that strong σ-donors, but they are even worse π-backbonding ligands. So the CO has virtually
no competition for π-backdonation. Based on CO IR stretching frequencies, the following ligands
can be ranked from best π-acceptor to worst:
NO+ > CO > PF3 > RN≡C > PCl3 > P(OR)3 > PR3 > RC≡N > NH3 56
σ/π Bridging CO

This is where the CO not only acts as a traditional σ-donor/π-acceptor to

one or more metal centers, but also as a π-donor to additional metals. This
will occur for more electron deficent metal complexes where the metal
centers have less need to π-backbond to the carbonyl, but have the empty
orbitals to accept electron density from the carbonyl π-system. The CO
ligand here can act as a 4 or 6 electron donor!
 2. Determination of Bond orders
Applications
• It has been seen that I.R. absorption frequency of ligated
1. Determination of geometries of Carbonyls CO is directly proportional to its B.O. In other words, the
through calculating number of IR active I.R. absorption band due to the stretching vibration of
bands ligated CO with a higher B.O. would occur at a higher
frequency and the I.R. absorption band of ligated CO with
a lower B.O. would occur at a lower frequency. Since the
absorption frequency for free CO is equal to 2250 cm─1
while that for ligated CO lies between 2220-1700 cm─1,
ligated CO has lower B.O. The lower B.O. is due to the
transfer of metal dπ electrons into the π* orbitals of ligated
CO. Let us study the following examples.
• Since the presence of positive charge on [Mn(CO)6]+
resists the flow of metal dπ electrons into the π* orbitals of
CO, the B.O. of CO increases. Due to the increase in B.O.,
the absorption band of ligated CO occurs at higher
frequency (= 2090 cm─1)

Metal Carbonyl [V(CO)6]─ [Cr(CO)6]─ [Mn(CO)6]+

Charge on Metal -1 0 +1
Absorption frequency for CO (cm─1) 1860 1980 2090 58
3. To differentiate between terminal and bridging carbonyl groups

4. To study reaction rates

The measurement of the rates of disappearance of the intensity of CO absorption bands in the I.R.
spectra can be used to study the rates of substitution reaction of metal carbonyls
5. Ligand Metal carbonyls are useful in organic synthesis and as catalysts or catalyst
6. Precursors in homogeneous catalysis, such as hydroformylation and Reppe chemistry.
H2 + CO + CH3CH=CH2 → CH3CH2CH2CHO
Dicobalt octacarbonyl acts as catalyst.
Co2(CO)8 could be used for hydrosilylation of olefins also.
7. In the Mond process, nickel carbonyl is used to produce pure nickel.
8. In organometallic chemistry, metal carbonyls serve as precursors for the preparation of other
59
ogranometallic complexes.
 Other Applications
Metal carbonyls are used in several industrial processes. Perhaps the earliest
application was the extraction and purification of nickel via nickel tetracarbonyl by the
Mond process.

❖Fe(CO)5 is used inter alia for the preparation of inductors, pigments, as dietary
supplements in the production of radar-absorbing materials in the stealth technology,
and in thermal spraying.
❖Metal carbonyls are used in a number of industrially important carbonylation
reactions. In the oxo process, an alkene, hydrogen gas, and carbon monoxide react
together with a catalyst (such as HCo(CO)4) to give aldehydes.
❖ Several other Metal-Carbonyl complexes have been employed in the
hydrocarboxylation and hydrogenation reactions.

60
Structure and Bonding Ferrocene
• Mössbauer spectroscopy indicates that the iron center in
ferrocene should be assigned the +2 oxidation state.
Each cyclopentadienyl (Cp) ring should then be
allocated a single negative charge. Thus ferrocene
could be described as iron(II) bis(cyclopentadienide)
Fe2+[C5H5- ]2.
• The number of π-electrons on each ring is then six,
which makes it aromatic according to Hückel's rule.
These twelve π-electrons are then shared with the metal
via covalent bonding. Since Fe2+ has six d-electrons, the
complex attains an 18-electron configuration, which
accounts for its stability. In modern notation, this
sandwich structural model of the ferrocene molecule is
denoted as Fe(η5-C5H5)2.
• Crystallography reveals that the cyclopentadienide
rings are in staggered conformation.
• Hybridization: d2sp3
61
• Magnetic Nature: Diamagnetic
Applications of Ferrocene
1. Fuel additives: Ferrocene and its derivatives could be used as antiknock agents in the fuel
for petrol engines. They are safer than previously TEL.

1. Pharmaceutical: Ferrocene derivatives have been investigated as drugs e.g. one drug has
entered clinic trials, Ferroquine (7-chloro-N-(2-((dimethylamino)methyl)ferrocenyl)quinolin-4-
amine), an antimalarial. Ferrocene-containing polymer-based drug delivery systems have
been investigated.

1. Solid rocket propellant: Ferrocene and related derivatives are used as powerful burn rate
catalysts in ammonium perchlorate composite propellant.

1. As a ligand scaffold: Chiral ferrocenyl phosphines are employed as ligands for transition-
metal catalyzed reactions. Some of them have found industrial applications in the synthesis of
pharmaceuticals and agrochemicals.
62
Fuel additive, smoke suppressant and chiral catalyst precursor

Ferrocene powder Ferrocene crystals

Ferox Gas & Diesel Fuel Additive

is a catalyst that is an eco-friendly
fuel additive and horsepower
booster. It allegedly increases
mileage from between 10 and 20%
while also significantly reducing
harmful emissions. 63
The Grignard Reagent
Grignard reagents are formed by the reaction of magnesium metal with alkyl or alkenyl halides.

They’re extremely good nucleophiles, reacting with electrophiles such as carbonyl compounds (aldehydes,
ketones, esters, carbon dioxide, etc) and epoxides.

They’re also very strong bases and will react with acidic hydrogens (such as alcohols, water, and carboxylic
acids).

64
 Applications of Grignard reagents ❖ Reaction with esters to give tertiary
❖ Reaction with aldehydes to form alcohols
secondary alcohols

❖ Reaction with epoxides

❖ Reaction with ketones to form tertiary

alcohols

❖ Reaction with CO2 to make carboxylic

acids
65
 Metals in biology

Contents……Metals in biology (haemoglobin, chlorophyll-

structure and property)
66
Chlorophyll- Structure and Property
❖ Structure of Chlorophyll
• Chlorophylls are green pigments with polycyclic, planar
structures resembling the protoporphyrin system
present in haemoglobin
• In chlorophyll, Mg2+ is the metal centre
• The four inward-oriented nitrogen atoms of the
porphyrin ring in chlorophyll are coordinated with the
Mg2+
• All chlorophylls have a long phytol side chain, esterified
to a carboxyl-group substituent in ring IV
• Chlorophylls also have a fifth five membered ring not
present in heme
• The heterocyclic five-membered ring system that
surrounds the Mg2+ has an extended polyene structure,
with alternating single and double bonds
• Such polyenes characteristically show strong absorption
in the visible region of the electromagnetic spectrum
• Chlorophylls have unusually high molar extinction
coefficients (higher light absorbance) and are therefore
particularly well-suited for absorbing visible light during 67
photosynthesis
❖ Chloroplasts always contain both chlorophyll a and
chlorophyll b
❖ Both are green, their absorption spectra are sufficiently
different that they complement each other’s range of light
absorption in the visible region
❖ Both chlorophyll a & b absorb in the blue and red region
so that the remaining green region is transmitted – hence
chlorophylls are green in colour
❖ Most plants contain about twice as much chlorophyll a
as chlorophyll b
❖ Chlorophyll is always associated with specific binding
proteins, forming light-harvesting complexes (LHCs) in
which chlorophyll molecules are fixed in relation to each
other, to other protein complexes, and to the membrane.

68
Role of Mg in chlorophyll
❖ Without Mg2+ the chlorin ring is fluorescent –
i.e. the absorbed light energy is emitted back
immediately
❖ With Mg2+ chlorophyll becomes
phosphorescent
❖ In the case of fluorescence, the absorbed
light energy is lost immediately – will not be
used for chemical reaction
❖ In the case of phosphorescence, there will
be excited state of finite life time and the
energy can be used for chemical
reactions
❖ The Mg2+ coordination increase the rigidity
of the planar chlorin ring: The energy loss
as heat due to vibration of the ring during
light absorption is prevented

69
Photosynthesis Reaction

Two types of photosystems

cooperate in the light reactions 70
A Photosynthesis Road Map

71
Hemoglobin Hb

Hb is not an exact Four units of Hb

tetramer of Mb

3 major types of Hb
Hb A (Adult)
Hb F (Fetal)
Hb S (Sickle cell)

72
❖ Each of these subunit polypeptides contains a heme
group—an iron atom at the center of a poryphyrin
ring—which reversibly binds a single O2 molecule in
the ferrous state (Fe2+).

❖ Whereas free heme binds O2 irreversibly and is

converted to the ferric state (Fe3+) in the process, Hb
can reversibly bind O2 because the valence state of
the iron atom is protected by encapsulating the heme
in the globin protein fold

❖ Each tetrameric (α2β2) Hb can therefore reversibly

bind four O2 molecules.

❖ Oxygenation changes the electronic state of the Fe2+

heme iron, which is why the color of blood changes
from the dark, purplish hue characteristic of venous
blood to the brilliant scarlet of arterial blood. 73
❖ The organic component of the heme group—
the protoporphyrin—is made up of four pyrrole
rings (A, B, C & D) linked by methine bridges
to form a tetrapyrrole ring. Four methyl
groups, two vinyl groups, and two proprionate
side chains are attached.
❖ The iron atom at the center of the
protoporphyrin is bonded to the four pyrrole
atoms.
❖ Under normal conditions the iron is in the
ferrous (Fe2+) oxidation state. The iron atom
can form wo additional bonds, one on each
side of the heme plane, called the fifth and
sixth coordination sites.
❖ The fifth coordination site is covalently bound
by the imidazole side chain of the globin chain
(the “proximal histidine,” α87 and β92).
❖ The sixth coordination site of the iron ion can
bind O2 or other gaseous ligands (CO, NO,
❖ CN−, and H2S
74
▪ Role of distal
histidine: Makes O2
to bind in a bent
fashion and makes it
difficult for CO to
bind in a linear
fashion.
▪ An isolated heme
binds CO 25000 times
as strongly as O2 in
solution. In the living
system binding affinity
for oxygen is reduced
considerably. For CO
to bind strongly, it has
Tense (T) state Relaxed (R) state
to bind linearly which
is made difficult by
distal histidine
75