Module-2: Metal complexes

and Organometallics
Prepared by:

Prof. Tapas Ghatak

Prof. A. Sheela
Prof. Madhvesh Pathak
Prof. G. Thirumanavelan
Prof. N. Palanisami
Prof. Akella Sivaramakrishna
Prof. G. Buvaneswari
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 Contents
Inorganic complexes - structure, bonding and application;
Organometallics – introduction, stability, structure and
applications of metal carbonyls, ferrocene and Grignard
reagent;
Metals in biology (haemoglobin, chlorophyll- structure and
property).

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Topic : Metal complexes: structure, bonding and
applications
 Chemists’ names for Complexes

• 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]

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 Double Salts and Co-Ordination Compounds

❖ Double Salt:
Ferric alum (NH4)2SO4.Fe2(SO)4.24H2O
- In water: NH4+, SO42-, Fe3+ 3Cl–
(counterion)
❖ Co-ordination Compounds
Fe(CN)2 + 4KCN Fe(CN)2.4KCN
ligand
(coordination sphere)

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

N forms a coordinate covalent bond

to the metal
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 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

6
 Chelating Agents

Bind to metal ions removing

them from solution.
Important biomolecules like heme
Phosphates are used to tie and chlorophyll are porphyrins
up Ca2+ and Mg2+ in hard
water to prevent them from
interfering with detergents.

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Coordination numbers and shapes of complex ions

8
 Werner's Theory: Alfred Werner,
Werner Coordination Theory Swiss chemist put forward a theory to
explain the formation of complex
compounds. It was the first successful
explanation, became famous as the
coordination theory of complex
compounds, which is also known as
Werner's theory.

Failure: 1. Bonding with in coordination

sphere.
2. Square planar (or) Tetrahedral
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 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
Provided the first electronic interpretation of bonding in coordination
compounds.
Coordination reaction between silver ions and ammonia illustrates that the
metal ion can be regarded as Lewis acid and the ligands as Lewis bases.

Denoted by an arrow pointing from the donor to the acceptor.

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 Sidgwick’s rule
Sidgwick’s Effective atomic number (EAN) rule : based on the
octet theory of Lewis this is the first attempt to account for the
bonding in complexes
EAN = The sum of the electrons on the central atom (Lewis acid) + No of
electrons gained or lost in ion formation + including those donated from the
ligands (Lewis base) = AN of next higher inert gas [Ni(CO)4], [V(CO)6]-
,
[Ni(CO)4] = 28-0+8 =36 (Next inert gas Kryption(AN-
36)
[Fe(CN)6]4- = 26-2+12 = 36
[Zn(NH3)4]2+ = 30-2+8 = 36
[V(CO) ] - = 23]3-+1+12=36
Exceptions: [Fe(CN) 2+
6 ; [Co(NH3)6]
6

Failure: Ionic nature of the complexes

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 Valence bond theory Linus Pauling, 1931
Valence Bond Theory predicts metal complex bonding arises
from overlap of filled ligand orbitals and vacant metal orbitals.
Resulting bond is a coordinate covalent bond.

Coordinati Geometry Hybrid Example

on number orbitals

2 Linear sp [Ag(NH3)2]+

4 Tetrahedral sp3 [CoCl4]2-

4 Square planar dsp2 [Ni(CN)4]2-

6 Octahedral d2sp3 or [Cr(H2O)6]3+,

sp3d2 [Co(H2O)6]2+
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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 electrons - paramagnetic and attracted by magnets
No. of d electrons=AN of central metal – number of electrons lost – AN of
previous inert gas (Argon -18) – for 1st and 2nd Transition series, For 3rd 14 has
to be substracted. Cu:29-2-18 = d9
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 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

No. of d electrons=AN of central metal – number of electrons lost – AN of

previous inert gas (Argon -18) – Ni: 28-2-18 = d8
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[Ni(CN)4]2-

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 Octahedral sp3d2 Geometry
Gives [CoF6]3– four unpaired electrons, which makes it
paramagnetic and is called a high-spin complex.
Ground state Co= (3d74s2)

No. of d electrons=AN of central metal – number of electrons lost – AN of

previous inert gas (Argon -18) – Co: 27-3-18 = d6
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 Octahedral d2sp3 Geometry
[Fe(CN)6]3- Fe: (3d64s2)

3d 4s 4p

Fe+3

[Fe(CN)6]3-

CN– Strong ligand d2sp3

No. of d electrons=AN of central metal – number of electrons lost – AN of
previous inert gas (Argon -18) – Fe: 26-3-18 = d5
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 Hybridization Magnetic behaviour

• The difference between sp3d2 and

d2sp3 hybrids lies in the principal
quantum number of the d orbital.

• In sp3d2 hybrids, the s, p, and d

orbitals have the same principal
quantum number—High Spin.
• In d2sp3 hybrids, the principal
quantum number of the d orbitals
is one less than s and p orbitals— Failures:
Low Spin. • Does not account for
• splitting of d-orbital
• A complex’s magnetic • spectra of complexes
properties determine which • Reaction rates and
mechanisms
hybrid is being used.
• Outer field (or) Inner field
• Tetrahedral (or) square planar
• Magnetic properties 18
 Bonding in Coordination Compounds
Many of the properties of metal complexes are dictated by their electronic
structures.

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.

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.

CFT provides better understanding of formation of complexes. However,

MO and LF theories, though more complicated, provides a more realistic
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perspective.
 Crystal Field Theory

Crystal field theory largely replaced VB theory for interpreting the chemistry
of coordination compounds.
Proposed by physicist Hans Bethe in 1929
Further modifications were proposed by J.H. Van Vleck in 1935 to allow for
some covalency in the interactions. These are referred to as Ligand Field
Theory
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.

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 CFT Assumptions
Interaction between the metal
ion and the ligands are purely
electrostatic (ionic)
Ligands are considered as
point charges
Ion-ion interaction, if the ligand
is negatively charged and ion- Interaction between electrons of the
cation and those of ligands are
dipole interaction, if the ligand entirely repulsive. This is responsible
is neutral for splitting of d orbitals.
Electrons on the metal are CFT does not consider the
overlapping between metal and
under repulsive from those on ligand orbitals.
the ligands d-orbitals loses their degeneracy
due to the approach of ligands
Electrons on metal occupy
during the formation of complex
those d-orbitals farthest away
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from the direction of approach
of ligands.
 Octahedral Complex

Ligands will interact with some d orbitals more In these orbitals, the ligands are between
than others the lobes, interact less strongly
Depends on relative orientation of orbital and
ligand
Ligands point right at lobes

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 Octahedral Field

d-orbitals in the isolated gaseous discrete point charges (ligands) are allowed
metal are degenerate. to interact with the metal, the degeneracy of
If a spherically symmetric field of the d orbitals is removed.
negative charges is placed around the Not all d orbitals interact with the six point
metal, these orbitals remain charges to the same extent.
degenerate, but all of them are raised Those orbitals along the axes will be
in energy as a result of the repulsion destabilized more than that of the orbitals
between the negative charges on the that lie in between the axes.
ligands and in the d orbitals.
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 Octahedral Complex and d-Orbital Energies

For the Oh point group, the x2-y2, z2 orbitals

belong to the Eg irreducible representation
and xy, xz, yz belong to the T2g
representation

The extent to these two sets of orbitals are

split is denoted by ∆0 or 10 Dq. As the
barycenter must be conserved on going
from a spherical field to an octahedral field,
the t2g set must be stabilized as much as the
eg set is destabilized.
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For d1-d3 systems: Hund’s rule predicts that
the electrons will not pair and occupy the t2g
set.
For d4-d7 systems (2 possibilities) : Either
pairing the electrons in t2g set (low spin or
strong field) or electrons in eg set, higher in
energy, but do not pair (high spin or weak
field).
Pairing energy (P) and eg-t2g splitting (∆0 or
10 Dq)

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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 27

(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

SMALLER Δ LARGER Δ

Complexes of cobalt (III) show

LONGER λ SHORTER λ the shift in color due to the
ligand.
(a) CN–, (b) NO2–, (c) phen, (d)
en, (e) NH3, (f) gly, (g) H2O, (h)
• For a given metal ion, the color depends on ox2–, (i) CO3 2–
the ligand.

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 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)
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 Effect of Ligand Field Strength on the Color of the Complexes

• Transition metal complexes are colored generally. Associated with the promotion of an electron
from one energy state to another. The energy required is obtained by absorbing light of a
particular wavelength.
• In transition elements, there are partially filled d levels. The d levels split into different energy
levels depending on the geometry of complex.
• To promote the electron from one d level to another d level which corresponds to a small
energy difference. This results in absorption of light of higher wavelength in the visible region
and the complex appear colored.
• The energy difference between split d levels in a transition element depends on nature of
ligand to a larger extent.
• Depending upon the CFSE, the light of difference wavelengths will be absorbed to effect d-d
transitions and hence the complexes have different colors depending upon the wavelength of
light absorbed.
• Complexes of s and p block elements are colorless. No d-d transition as all the d levels are doubly
occupied. The energy required to remove an electron from s or p level to a higher level is much greater.
This may correspond to UV region, in which case it is colorless.
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 Chemistry of Colors
Thus, the Ligand Field Strength is related to the Color of the Complexes
[Cu(H2O)4]2+ : light blue ; [Cu(NH3)4]2+ : deep blue ; [CuCl4]2- : yellow ; [Cu(en)2]2+ :
violetcolorless
In all the above complexes, Cu is in +2 oxidation state, but the ligand field strength
differ. Hence they have different colors.
d-d transitions take place by the absorption of visible radiation by transition metal
ions and transmitted light is colored with the complementary color of the color of the
light absorbed. e.g., when red-light is removed from the white light, the eye
sees its complementary color – blue-green.

Color of various Ni(II) complexes in aqueous

solutions
From left to right, hexaamminenickel(II) -
[Ni(NH3)6]2+;
tris(ethylenediamine)nickel(II) -
[Ni(en)3]2+ ; tetrachloronickelate(II) -
[NiCl4]2- ; hexaaquanickel(II) -
[Ni(H2O)6]2+.
Reactions starting from NiCl2·6H2O can
be used to form a variety of nickel31
coordination complexes because the
H2O ligands are rapidly displaced.
[Co(NH3)6]3+ [Co(en)3]3+ [Co(NO2)6]3- are orange yellow while [CoF6]3- [Co(H2O)6]3+ are
blue
• Co3+ = 27-3-18 = d6
• NH3, en and NO2 are strong field ligands (more splitting – (t2g)6 (eg)0 - Large ∆o)
• To favour d-d transition, the energy required is high. Hence absorbs violet color or blue
color and will appear yellow or orange.
• F- and H2O are weak field ligands (less splitting - (t2g)4 (eg)2 - small ∆o)
• Because of small ∆o, lower energy radiations are required for d-d transition. The
complex absorbs yellow or orange (lower energy) and appear as blue.

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33
Colors of Coordination Complexes

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 Charge-Transfer (CT) Bands
Metal d-orbitals are involved in charge-transfer (CT) transitions too as like d-d transitions
Observed when filled empty ligand- and metal-centered orbitals have similar energies
Occurs due to the movement of electrons between metal and ligand. Often stronger than d-d bands

Direction of the electron transfer is determined by the relative energy levels of these orbitals:
i) Ligand to Metal (LMCT) - MnO4-, CrO42-
MnO4-, the d-electron count on Mn(VII) is d0. The origin of the color in this species is not
due to d-d transition, rather, charge transfer from O2- to Mn(VII), described as LMCT band.
Favored when metal is in high oxidation state attached to ℼ-donor ligands such as oxide,
hydroxide, fluoride.

ii) Metal-to Ligand (MLCT) - [Fe(bpy)3]2+ - charge transfer occurs from Fe(II) to the empty π*
orbitals of bpy ligand. Favored in electron rich metal centers attached to ℼ-acceptor
ligands. Bands occur in UV region (higher in energy) – metal carbonyls

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 Tetrahedral Crystal Field
Imagine a tetrahedral molecule inside a cube with metal ions in
the center of the cube. The ligands occupy the four alternate
corners of the cube leaving the rest four corners empty.
Tetrahedral complex - ∆t is relatively small even with strong field
ligands as there are fewer ligands to bond with.
Usually, electrons will move up to the higher energy orbitals rather
than pair. Because of this, most tetrahedral complexes are high
spin.

The two ‘e’ orbitals point to the center of the face of the
cube while the three ‘t2’ orbitals point to the center of the
edges of the cube.
Therefore, the angle between the e orbitals, metal and
ligand is 54o44’. But the angle between the t2 orbitals, metal
and ligand is 35o16’.
Thus the t2 orbitals are nearer to the direction of approach of
the ligands than the e orbitals.
Hence, t2 orbitals have higher energy compared to e-
orbitals. 36
 Tetrahedral Crystal Field
Position of four ligands with respect to the d orbitals of the central metal ion.
• The d orbitals having their lobes oriented in between the axes (t2 orbitals)
are nearer to four ligands. Hence interact with the ligand orbitals to a
greater extent and hence higher energy.
• whereas the two d orbitals having their lobes oriented along the axes (e)
are away from the ligands. Interact only to a lesser extent with the ligand
orbitals.

Splitting of d orbitals just the reverse of splitting observed in oh complexes.

Difference in energy -tetrahedral crystal field splitting energy [∆t = (4/9) ∆0]
Reason:
Only 4 ligands. Hence 1/3rd decrease in the number of ligands decreases the ∆t
High energy t2 orbitals although nearer to the ligands, do not point directly to
the ligands. Hence the extent of interaction is less. But in oh complex, the eg
orbitals point directly at the ligands.
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 Tetrahedral Crystal Field

= −0.4 x n(t2) + 0.6 x n(e)

∆o

= -0.6 x n(eg) + 0.4 x

n(t2g)

All tetrahedral complexes are high spin since the CFSE is smaller than the pairing
energy.
Low spin configurations are rarely observed.
If a very strong ligand is present, the square planar geometry will be favored.
38
= -0.6 x n(eg) + 0.4 x
n(t2g)

39
40
Square Planar Crystal Field

Note: Whichever orbitals

come in direct contact with
the ligand fields will have
higher energies than
orbitals that slide past the
ligand field and have more
of indirect contact with the
ligand fields.
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Consequences of Crystal Field Splitting

42
Ionic radii of transition metals in complexes

43
44
45
46
 Site Preference for Spinels and Inverse Spinels

• Based on CFSE values, it is possible to predict the type of compounds having

the formula AB2O4 whether it belongs to normal spinels or Inverse Spinels
47
 Merits of crystal Field Theory

Predict most favorable geometry of a complex

Accounts for four coordinated complexes (tetrahedral and square

planar)

Explains the ligands forming outer / inner orbital complexes (high

spin / low spin)
Interprets magnetic properties taking in to consideration the orbital
contributions also

Interprets color of transition metal complexes

Explains spectral properties of many transition metal complexes

48

Predict site selection in spinel and antispinel structures

 Limitations of CFT
CFT considers only the metal ion d-orbitals and gives no consideration at all to
other metal orbitals such as s-, p-orbitals and the ligand π-orbitals. Therefore, to
explain all the properties of the complexes dependent on the π-ligand orbitals
will be outside the scope of CFT. This does not consider the formation of π-
bonding in complexes.

Less accurate when covalent bonding increases or partly covalent nature

of the metal-ligand bonds (As ligand orbital and electrons become more
important). Bonding strength and chemical properties cannot be explained in
some complexes based on only electrostatic interactions (purely ionic) as
assumed by the theory

CFT is unable to account satisfactorily for the relative strengths of ligands,

e.g. it gives no explanation as to why H2O appears in the spectrochemical
series as a stronger ligand than OH-
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 Preparation of Complex Compounds

Complexes are prepared by the following types of

reactions:

Connection Reactions:
HgI2 + 2KI K2[HgI4]

Substitution Reactions:
[Cu(H2O)4]SO4 + 4NH3 [Cu(NH3)4]SO4 + 4H2O

Exchange Reactions:
2ZnCl2 + K4[Fe(CN)6] Zn2[Fe(CN)6] + 4KCl

Redox Reactions:
2Al + 6KOH + 6H2O K3[Al(OH)6] + 3H2 50
 Properties of Complex Compounds
Dissociation of complexes: Complexes are strong electrolytes.
Readily dissociate to a complex ion and the counter ion – Primary
dissociation
[Ag(NH3)2]Cl [Ag(NH3)2]+ + Cl-
Formed complex ion may also dissociate – weak dissociation –
Secondary dissociation [Ag(NH3)2]+ Ag+ + 2 NH3

Stability of complexes: Formation constant (Kf) describes the

formation of complex ion from central metal and the ligands attached to
it
Known as stability constant or association constant.
M + 4L ML4 β4 = [ML4] / [M] [L]4

Stepwise stability constant (Kn) and overall stability constant (βn) are
therefore related as follows. βn = K1 K2 K3 K4…….Kn
51

Dissociation constant is the reciprocal of formation constant

 Stability of Complex Compounds
Formation constant (Kf) describes the formation of complex ion from
central metal and the ligands attached to it. Known as stability constant or
association constant
Kf can be explained simply as given below, where M is a metal ion, L is a
ligand and x and y are coefficients.
Larger the Kf value of a complex ion, greater the stability

Experimental methods - potentiometry, voltammetric methods (polarography

and anodic stripping voltammetry), pH-metry, spectophotometric methods,
and nuclear magnetic resonance spectroscopy.
pH-metry is the most sensitive and accurate of all the methods
Extraction metallurgy, nuclear energy industry, analytical methods,
and medical, environmental, and industrial research.
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The above applications require stability constant values of high reliability
 Application 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.
• Extraction of metal
• Analytical chemistry
• Biological importance
• Medicinal application
• Industrial application
• Hardness estimation
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 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.

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 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

56
 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
systems)
Metalloprotein with the metal ion cofactor have many diverse functions including
transport, storage, and signal transduction.

Heme B: Heme B is a porphyrin (four linked pyrrole rings)

that readily binds iron, as shown. This is an example of a
biomolecule that contains non-protein ligands for a
transition metal.

57
 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.

58
 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 β-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. 59
 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
60
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.

61
Organometallics – Introduction, stability,
structure and applications of metal carbonyls,
ferrocene and Grignard reagent

62
Organometallic
Chemistry
❖ An area which bridges organic and inorganic chemistry
❖ A branch of coordination chemistry where the complex
Zeise’s
has one or more metal-carbon bonds dicobalt (0)
Salt octacarbonyl

❖ What is organometallic compounds?

Edward Frankland coined the term “Organometallic”
o The designation “Organometallic” generally denotes compounds in which organic groups are
linked directly to the metal through at least one carbon atom.
o Metal hydrides are often included, H being considered as the "smallest organic group"
❑ Therefore:
• Ti(OC4H9)4, Ca{N(CH3)2}2 and Fe(SC5H11)3 are not considered as organometallic
• However, C6H5Ti(OC4H9)3, and (C5H5)2Zr(OOCCH3)2 would be organometallic
As in many other areas of chemistry, there are some obvious exception to this simple
definition of organometallic compounds; for example, in spite of species like CaC2, Hg(CNO)2,
[Fe(CN)6]4- having metal-carbon bonds, these are not considered organometallic compounds
for traditional or/and some other obvious reasons!
What all compounds are considered as Organometallic?

C always 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.
❖ It is also understood that the element to which carbon is bound is more electropositive than
carbon in organometallic chemistry.
❖ Traditional chemists do not agree for classifying metal cyanide complexes as
organometallic
64
History of Organometallic
Compounds Cacodyl (tetramethyldiarsine) was
1760 Cacodyl As2(CH3)4 probably the first organometallic derivative
isolated by Prussian military apothecary

The first transition metal organometallic Zeise's Salt K+[(C2H4)PtCl3]– 1827

compound

Grignard Reagents
1900 RMgX
Awarded Nobel Prize in 1912

Gilman Reagents R2Cu–Li+ 1930

1951 Ferrocene Awarded Nobel Prize in 1973

65
Zeise’s Salt- The first transition metal organometallic
compound

❖ Discovery 1827
❖ Structure ~ 150 years later

W. C. Zeise, Danish
pharmacist, I789- I847
‘The breakthrough, the isolation of a pure, crystalline compound came when Zeise
Also father of the added potassium chloride to a concentrated PtCl4 /ethyl alcohol reaction solution
chemistry of and evaporated the resulting solution. Beautiful lemon yellow crystals, often one
mercaptans R-SH half inch or more in length were isolated. On longer exposure to air and light, they
gradually became covered with a black crust. They contained water of hydration,
which was lost when they were kept over concentrated sulfuric acid in vacuo or
when heated to around 100°C. Chemists in those days often reported how the
compounds that they had prepared tasted. Zeise described the taste of this
potassium salt as metallic, astringent and long lasting.’
Dietmar Seyferth, Organometallics, 2001, 20, 2 66
First organometallics in homogeneous catalysis- The
Hydroformylation (1938)

Otto Roelen First Industrial plant-

Pioneer in Industrial hydroformylation
homogeneous catalysis
(1897-1993)

detergents
67
First σ-bonded Organometallic Compound-
Diethyl zinc
3 C2H5I + 3 Zn → (C2H5)2Zn + C2H5ZnI + ZnI2

❖ Student of Robert Bunsen (Bunsen burner fame!).

Prepared diethyl zinc while trying to make ethyl
radicals.

Edward Frankland
1825-1899

Frankland coined the

term “Organometallic”

As the early 1850s English chemist Edward Frankland described flasks exploding,
throwing bright green flames across his lab, as he heroically distilled dialkylzinc
compounds under an atmosphere of hydrogen.
68
Nobel Prizes in Organometallic Chemistry
Ziegler-Natta polymerization
TiCl3 and (CH3CH2)3Al

1963
Olefin Metathesis
❖ 1963: Zeigler and Natta Grubbs-Schrock-Chauvin
❖ 1973: Wilkinson and E.
O. Fischer 2005
❖ 1976: W. Lipscomb
❖ 1979: Herbert Brown, G. Cross Coupling
Wittig
❖ 1981: Fukui and R. Heck-Negishi-Suzuki
Hoffman
❖ 2001: Sharpless, 201
Knowles and Noyori 0
❖ 2005: Schrock, R. H.
Grubbs, and Chauvin
❖ 2010: Heck, Negishi and
Suzuki 69
Why the subject is
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
orbitals 70
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 71
General Periodic Trends of Organometallic
Compounds

Group 1 Except lithium, ionic compounds

Li, Be, Mg, B, Al Covalent and multi centre (e.g., 2e-3C ) bonds
Group 2-11 M-C bond : σ-bond (e.g., B-CH3)
π-bond ((e.g. (CO)5Cr=CH2)
δ-bond ([R4Re ≡ ReR4]2-)
η-bond (e.g., Cp2Fe)
Lanthanides M-C bond predominantly ionic
Actinides M-C bond predominantly covalent
Group 12-16 mainly M-C σ bonds

72
Some Important Ligand
Nomenclature
“eta-x” was originally developed to indicate how many carbons of a π-system were

η 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.
x
• 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

73
 “mu-x” is the nomenclature used to indicate the presence of a bridging ligand

µx
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.
Ordering There is no set method of naming or ordering the listing of metal and ligands in a
metal/ligand complex that most authors follow. There are IUPAC formalisms, but hardly anyone
follows them. There are some qualitative rules that most authors seem to use in American
Chemical Society (ACS) publications:
1) in formulas with Cp (cyclopentadienyl) ligands, the Cp usually comes first, followed by the
metal center: Cp2TiCl2
2) other anionic multi-electron donating ligands are also often listed in front of the metal
3) in formulas with hydride ligands, the hydride is sometimes listed first. Rules # 1 & 2, however,
take precedence over this rule: HRh(CO)(PPh3)2 and Cp2TiH2
4) 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

74
Stability of Organometallic
Compounds

75
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.

❖ Most metal alkyls and aryls, MRn, are thermodynamically unstable to oxidation and
hydrolysis and, therefore, need protection from the atmosphere during their synthesis,
isolation and storage.

❖ There are few other examples of organometallic compounds like tetramethyllead

which are thermodynamically unstable with respect to oxidation and hydrolysis, yet
they survive exposure to air or/and moisture possibly because of kinetic factors.
76
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 77
Stability to
Oxidation
❖ The thermodynamic instability of organometallic compounds may be ascribed to the large
value of free energies of formation of the metal oxides, carbon dioxide and water. Actually the
combustion of organometallic compounds is a highly exothermic process, e.g.,

Zn(CH3)2 (g) + 4O2(g) → ZnO(s) + 2CO2(g) + 3H2O(g)

ΔH*m = ─1918 kj mol─1
Sn(CH3)4 (g) + 8O2(g) → SnO2(s) + 4CO2(g) + 6H2O(g)
ΔH*m = ─3591 kj mol─1
❖ It is worth noting that dimethylzinc is a spontaneously inflammable compound whereas
tetramethyltin is air stable. The greater reactivity of dimethylzinc can be easily understood on
the basis of its strong Lewis acid character. In addition to ZnMe2, the lighter alkyls of Li, Na,
Be, Mg, Zn, B, Al, Ga, In, Tl, As, Sb and Bi are also spontaneously inflammable. Thus the
presence of empty low-lying orbitals (e.g., 4p orbital of GaMe3) or a lone pair of electrons (as
in SbMe3) appears to be a source for kinetic reactivity to oxidation by air. The Group IVB
tetraalkyis such as SnMe4 possess neither of these characteristics and, therefore, they resist
oxidation at ambient temperatures.
78
Stability to
Hydrolysis
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

As a consequence of these factors, the organoderivatives of alkali and

alkaline earth metals as well as of Zn, Cd, Al, Ga and In are readily
hydrolyzed. By contrast, the trialkylboranes although coordinatively
unsaturated (the empty 2p orbitals on the boron atom provides a site for
nucleophilic attack) are unaffected by water at ambient temperatures,
possibly due to comparatively very low polarity of boron-carbon bonds. The
alkyls and aryls of the Group IV and V elements are also kinetically inert to
hydrolysis by water. 79
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
sites). 80
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!

81
• 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.

82
Classification of Organometallic
Compounds
❖ Organometallic compounds are classified in 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 compound are (CH3)4Sn, (C2H5)4Pb, Al2(CH3)6, Al2(C2H5)6, Pb(CH3)4 etc.
(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. 83
 (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.

Ni(CO)4 Fe(CO)5 Cr(CO)6 Fe(CO)9

84
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 formulas of coordination compounds are ‘complex’ ─ for example, CoCl3·6NH3, which in Warner’s term,
has the primary valence satisfied by Cl- and secondary valence satisfied by NH3. The nature of secondary
valence follows from G. N. Lewis’s treatment of the coordinate covalent bond in which the ligand atom
furnishes an electron pair that is shared with the central metal ion. Sidgwick argued that coordination process
provided the opportunity for the transition metal ion to reach a noble gas configuration. The effective atomic
number (EAN) of a metal ion is calculated by adding the electrons of the metal ions to those shared with it
through coordination. This electron-counting scheme is also called “eighteen-electron 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”
85
Counting
electrons
There are two models for counting electrons. Both give the same answer, but offer different
advantages and disadvantages.
Example: CH4
❖ Covalent model: Since C-H bonds are ❖ Ionic model: Alternatively, we can treat the
covalent, assume that the electrons are bonds as being ionic. This allows us to
shared equally between carbon and assign a formal oxidation state to the
hydrogen. To count the electrons, we carbon atom. This can be useful to
dissect the molecule giving each atom 1 determine whether a particular
electron of the bonding pair. transformation is an oxidation or a
reduction. In this model, both electrons are
given to the atom with the higher
electronegativity. For a C-H bond, this is the
carbon.

H: 4 × 1e = 4e H+: 4 × 0e = 0e
C: 4e C (-4): 8e
Total = 8 electrons Total = 8 electrons
86
Counting electrons for metal
complex
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. See the table below.

In my opinion, the ionic model is easier and gives a clearer picture of the actual chemistry,
since the formal oxidation state is part of the calculation. All discussions in this class will
use the ionic model, so I would encourage you to learn that one. You should also be
aware of the covalent method, since you will encounter it from time to time!
87
To determine the electron count for a metal
complex
1) Determine the oxidation state of the transition metal center(s) and the metal centers
resulting d-electron count. To do this 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)
2) Add up the electron counts for the metal center and ligands

❖ Complexes with 18 e- counts are referred to as saturated, because there are no

empty low-lying orbitals to which another incoming ligand can coordinate.
Complexes with counts lower than 18e- are called unsaturated and can
electronically bind additional ligands.

o Let’s take an example and try to understand stepwise (Next page)!!

88
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.

89
 Ligand Covalent Model Ionic Model
Electron count Charge Electron Count
η2(σ)-Dihydrogen 2 0 2
Hydride 1 -1 2
Halide (F-, Cl-, Br-, I-) or pseudohalide (-CN, 1 -1 2
-OTs, etc)
CO, CNR (bridging or terminal) 2 0 2
PR3, AsR3, SbR3, NR3, imines, nitriles, 2 0 2
ethers, sulfides, etc.
Terminal dinitrogren (N2) 2 0 2
η2(π)-Alkene 2 0 2
η2(π)-Alkyne 2 or 4 0 2 or 4
η2(π)-Carbonyl 2 0 2
η6(π)-Arene 6 0 6
η1-Acyl 1 -1 2
η2-Acyl 3 -1 4
η3-Allyl 3 -1 4
η5-Cyclopentadienyl (Cp-) 5 -1 6 90
 Ligand Covalent Model Ionic Model
Electron count Charge Electron Count
Imide (M=NR) 2 -2 4
Oxide (M=O) 2 -2 4
Peroxide (terminal or bridging) 2 -2 4

Alkylidine or carbyne, terminal M≡C-R 3 -3 6

Nitride (M≡N) 3 -3 6
Nitrosyl (linear, NO+), terminal or bridging) 3 +1 2
Halide (X─) µ-bridging 3 -1 4 (2 to each
metal)
Alkoxide, thiolate, amide, phosphide: OR−, 1 -1 2
SR− , NR2─ , PR2─
η4-acyclic diene 4 0 4

91
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 is neutral), and since we have one anionic ligand
present, the Re metal atom must have a +1 charge
to compensate for the one negatively charged Now we can do our electron counting:
ligand. The +1 charge on the metal is also its
Re(+1) d6
oxidation state. So the Re is the in the +1 oxidation 2 PR 4e-
3
state. We denote this in two different ways: Re(+1),
2 CO 4e-
Re(I), or ReI. I prefer the Re(+1) nomenclature
CH3− 2e-
because it is clearer. Most chemistry journals,
CH2=CH2 2e-
however, prefer the Roman numeral notation in
parenthesis after the element. Total: 18e- 92
Example 2
1) There is a +2 charge on the
complex
2) The CNCH3 (methyl
isocyanide) ligand is neutral, but
lets check the Lewis Dot
structure to make sure that is
correct:
Nitrogen is normally trivalent, that is, it wants to have 3 Now we can do our electron
chemical bonds to it. When it has 4 bonds, one more than counting:
usual, the nitrogen atom is assigned a formal positive charge.
Carbon, on the other hand, is tetravalent and almost always
Mo(+2) d4
wants 4 bonds. In isocyanides, however, we only have 3 bonds
7 CNCH3 14e-
to the C. To keep an even number of electrons around the C
we add an extra electron and the carbon gains a formal Total: 18e-
negative charge.
3) Because there is a +2 charge on the complex and there are
all neutral ligands present, the Mo has a +2 charge & oxidation
state. 93
More Examples

94
HMn(CO)5
Mn(+1) d6 6e-
5 CO 10e-
H− 2e-
Total: 18e-

95
Exceptions to the 18 electron
rule
❖ Square planar organometallic complexes of the late transition metals
(16e).
• Some organometallic complexes of the early transition metals (e.g.
Cp2TiCl2, WMe6, Me2NbCl3, CpWOCl3) [ A possible reason for the same is
that some of the orbitals of these complexes are too high in energy for
effective utilization in bonding or the ligands are mostly σ donors
❖ Some high valent d0 complexes have a lower electron count than 18
❖ Sterically demanding bulky ligands force complexes to have less than 18
electrons
❖ The 18 electron rule fails when bonding of organometallic clusters of
moderate to big sizes (6 Metal atoms and above) are considered
❖ The rule is not applicable to organometallic compounds of main group
metals as well as to those of lanthanide and actinide metals
96
❖ There are quite a few examples of organometallics which have 16 VE. As with all chemistry,
the excuse is either electronic or steric (or both).

(i) Electronic effects (ii) Steric Effects

Late transition metals with d8 electron Early transition metals have fewer d-
configurations e.g. Rh(I), Ir(I), Pd(II), Pt(II) have electrons to start with than the middle and
a strong tendency to form square planar 16 VE late transition metals, so they must achieve
complexes. Similarly, d10 complexes tend to their 18e count by coordination of a larger
form trigonal 16 VE complexes. As the atomic number of ligands. If the ligands involved are
number Z increases, the d-shell is stabilized too bulky, then low-electron count
(lowers in energy). The occupied dz2 orbital complexes are formed.
(perpendicular to the plane) is no longer
involved in ligand bonding.

97
❖ For early transition metals (e.g. with d0 metals) it is often not possible to fit the number of
ligands necessary to reach 18 electrons around the metal.

98
Unique reactions in organometallic
chemistry
Oxidative Addition
Reductive Elimination
Migratory Insertion
Transmetallation
β - Hydride Elimination

99
Common Reactions
❖ 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! 100
❖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). 101
❖ Migratory
AInsertion
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.
102
❖ Transmetallati
on
Definition: the transfer of 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
103
❖ β-Hydride
AElimination
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). 104
Metal Carbonyls and Ferrocene

105
MO Diagram of CO:

106
Carbonyl Ligands

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

107
Introduction
❖ Metal carbonyls are coordination complexes of transition metals with carbon monoxide
ligands in low oxidation state where CO ligand acts as neutral ligands
❖ Metal carbonyl compounds were first synthesized in by Paul Schützenberger in 1868 by
passing chlorine and carbon monoxide over platinum black, where
dicarbonyldichloroplatinum [Pt(CO)2Cl2] was formed
❖ Although many compounds were produced, they couldn’t be fully characterized until
❖ the development of X-ray diffraction, IR and NMR spectroscopy.
❖ In general, these compounds obey the “18 electron rule.”
❖ Normally diamagnetics, Most metal carbonyls are toxic.
❖ Monomerics are colourless, whereas polymerics are coloured.
❖ Poor conductors of electricity and Sublimated at low temperature.
❖ Soluble in organic solvents

108
Classification

109
Preparation
❖ Direct reaction of metal with carbon
monoxide
Ni + 4 CO → Ni(CO)4 (1 bar, 55 °C)

Fe + 5 CO → Fe(CO)5 (100 bar, 175 °C)

❖ Reduction of metal salts and oxides

CrCl3 + Al + 6 CO → Cr(CO)6 + AlCl3

❖ Preparation of dinuclear carbonyls from mononuclear carbonyls (Photolysis and

thermolysis)
2Fe(CO)5 → Fe2(CO)9 + CO

110
111
Chemical properties
1. CO substitution
M(CO)n → M(CO)n-1 + L → M(CO)n-1L

2. Reduction
Mn2(CO)10 + 2 Na → 2 Na[Mn(CO)5]
Fe(CO)5 + 2 Na → Na2[Fe(CO)4] + CO

3. Nucleophilic attack at CO
Fe(CO)5 + NaOH → Na[Fe(CO)4CO2H]

4. With electrophiles
Fe(CO)5 + X2 → Fe(CO)4X2 + CO

112
Structure of CO According to VBT & MOT
❖ Molecular Orbital Diagram for CO

A simple MO diagram for CO is shown above. The highest occupied

molecular orbital (HOMO) is indicated by the pair of electrons. This is
the 5σ lone pair orbital mainly centered on the carbon and weakly
antibonding with respect to the C-O bond (although that isn’t too clear
from the orbital contour plot). The LUMO is strongly π* antibonding
and is low enough in energy to act as a good acceptor orbital for
interacting with filled d-orbitals on metals. 113
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
atom with antibonding pi orbitals on CO molecule. 114
Structure of Ni(CO)4

115
Structure of
Fe2(CO)9

116
Carbonyl IR Stretching Frequencies
❖The position of the carbonyl bands in the IR depends mainly on the bonding mode of
the CO (terminal, bridging) and the amount of electron density on the metal being π-
backbonded to the CO.
❖ The number (and intensity) of the carbonyl bands one observes depends on the
number of CO ligands present and the symmetry of the metal complex. There are also
secondary effects such as Fermi resonance and overtone interactions that can
complicate carbonyl IR spectra.
❖ Bonding Modes:
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.
Note that these ranges are typical for
“neutral” transition metal complexes
with an average amount of electron
density on the metal center (see
discussion in next page). Bridging
carbonyls tend to have weaker and
broader IR bands. 117
Effect of Electron Density on Metal
❖ As the electron density on a metal center
increases, more π-backbonding to the CO
ligand(s) takes place. This further weakens
the C-O bond by pumping more electron
density into the formally empty carbonyl π*
orbital. This increases the M-CO bond
strength making it more double-bond-like, i.e.,
the resonance structure M=C=O assumes
more importance. This can clearly be seen on
the table to the right that illustrates the effect
of charge and electronegativity on the amount
of metal to CO π-backbonding and the CO IR
stretching frequency.

118
More examples
Shown below is another example of the dramatic effect on the νCO IR stretching frequencies on
reducing Fe2(μ-PPh2)2(CO)6 by 2 electrons to form the dianionic complex [Fe2(μ-PPh2)2(CO)6]2−.
The average νCO frequency shifts almost 150 cm−1 to lower energy on reduction.

119
More examples
The carbonyl region in the IR spectrum can be very distinctive and useful for help in assigning
structures and for indicating the relative amount of electron density present on the metal:

120
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 121
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!

122
 2. Determination of Bond orders
Applications • It has been seen that I.R. absorption frequency of
1. Determination of geometries of ligated CO is directly proportional to its B.O. In other
Carbonyls words the I.R. absorption band due to the stretching
Calculating number of IR active bands vibration of ligated CO with a higher B.O. would occur
with Raman active bands and then tally at a higher frequency and the I.R. absorption band of
with number of bands predicted ligated CO with a lower B.O. would occur at a lower
theoretically 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 123
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 hydrosilation 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
124
ogranometalic complexes.
125
Sandwich Compounds
The hapto symbol, η, with a numerical superscript, provides a topological description by
indicating the number of carbon atoms at a bonding distance to the metal
Sandwich

(η5-C5H5)2Fe (η6-C6H6)2Cr

G. 1973 Nobel Prize E. O.

126
Wilkinson ‘sandwich compounds’ Fischer
Ferrocene’s Applications: 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. 127
Ferrocene
• It is popular Organometallic compound with the formula Fe(C5H5)2.

• The molecule consists of two cyclopentadienyl rings bound on opposite sides of a

central iron atom.

• It is an orange diamagnetic solid and is soluble in most organic solvents e.g. C6H6.

• It is remarkable for its stability: unaffected by air, water, strong bases, can be heated
to 400 °C without decomposition, m. p. 174 0C

• Preparation:

• 2C5H5MgBr + FeCl2 → Fe(C5H5)2 + MgBr2 + MgCl2

128
Structure and Bonding
• 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
129
• Magnetic Nature: Diamagnetic
Chemical reactions of Ferrocene
❖ Friedel crafts Acylation
Ferrocene and acetyl chloride in the equimolar quantities give the mono substituted derivative
while in the double quantities resulted in distributed derivatives

❖ Friedel crafts Alkylation ❖ Mannich condensation

130
Importance
• Ferrocene was not the first organometallic compound known. Zeise's salt
K[PtCl3(C2H4)]·H2O was reported in 1831.
• Mond's discovery of Ni(CO)4 occurred in 1888 and organolithium compounds were
developed in the 1930s.
• However, it can be argued that it was ferrocene's discovery that
began organometallic chemistry as a separate area of chemistry. It also led to
an explosion of interest in compounds of d-block metals with hydrocarbons.
• The discovery was considered so significant that Wilkinson and Fischer shared the
1973 Nobel Prize for Chemistry "for their pioneering work, performed independently,
on the chemistry of the organometallic, so called SANDWICH compounds.”
• The rapid growth of organometallic chemistry is often attributed to the excitement
arising from the discovery of ferrocene and its many analogues (metallocenes).

131
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.
132
The Grignard
Reagent He was the student of Philippe Barbier (Barbier reaction [Zn]) He
discovered the Grignard reaction [Mg]) in 1900. He became a professor
at the University of Nancy in 1910 and was awarded the Nobel Prize in
Chemistry in 1912.

François Auguste
Victor Grignard
1871-1935

133
• 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).
❖ Preparation of Grignard reagents
• Grignard reagents are made through the
addition of magnesium metal to alkyl or
alkenyl halides. The halide can be Cl, Br, or
I (not F). It’s slightly easier to make
Grignards from the iodides and bromides,
however. Note what’s happening here – the
magnesium is “inserting” itself between the
carbon and the halide. This halide the “X”
referred to when we refer to Grignard
reagents as “RMgX”.

134
 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
135
 Reaction Mechanism
How it works: Addition to
aldehydes/ketones Grignard
reagents are extremely
strong nucleophiles – the
electrons in the C─Mg bond
are heavily polarized toward
carbon

136
Metals in
biology

137
Essential metal ions and their
functions

A biological periodic table of the elements indicating the essential elements. The essential elements for most forms of
life are shown in black with the exception of chromium (Cr), which is shown with an upward diagonal pattern, and
essential elements that are more restricted for some forms of life shown in gray. 138
• Most living organisms require some 25 elements.
• In the case of Homo sapiens, there are 10 essential metal ions (sodium, potassium, calcium, magnesium,
manganese, iron, cobalt, copper, zinc, and molybdenum).
• Of these, the first four are considered as “bulk elements” (Na+, K+, Ca2+, and Mg2+), representing 112 g, 160 g, 1.1
kg, and 25 g, respectively, in an “average” person of body weight 80 kg Together, they constitute some 99% of the
metal ion content of the human body.
• The others, manganese, iron, cobalt, copper, zinc, and molybdenum, designated “trace elements,” are present in
much lower amounts than the bulk elements (respectively, 16 mg, 4.8 g, 1.6 mg, 80 mg, 2.6 g, and 8 mg in an 80-kg
person).
• The essential alkali metal ions Na+ and K+ only weakly bind organic ligands,
rendering them extremely mobile, as with H+ and Cl-. This enables them to
generate ionic gradients across biological membranes.
• The alkaline earth metal ions, Mg2+ and Ca2+, have
greater binding strengths to organic ligands than Na+
and K+, and therefore are less mobile. Both play
important structural and catalytic roles, with 99% of the
body’s Ca2+ found in bone and teeth.

Hemoglobin
Myoglobin Vit Carbonic
Cytochromes B12 Hemocyani anhydrase 139
Ferredoxin n Carboxypeptidas
e
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 140
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.

141
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
142
Mg(II) prefers tetrahedral geometry rather than square planar geometry. But in Chlorophyll it is in
square planar geometry
So Mg(II)-N bonds in chlorophyll is strained – the electrons involved in bonding can be excited upon
light absorption as strain is relived in excited state
Antenna chlorophylls–polymers of chlorophyll are formed due to the coordination of the carbonyl part
one chlorophyll with Mg(II) of other chlorophyll. The polymer is terminated when there is water
coordinated with Chlorophyll at axial position
The coordination of water in the axial position with Mg(II) favours splitting of water to form H atom
that provides electron for photosynthetic process – active reaction centre in photosynthesis
Active reaction Antenna
centre in chlorophyll
photosynthesis

This transformation
provides electron required
for photosynthesis reaction

143
Photosynthesis
Reaction

Two types of photosystems

cooperate in the light reactions 144
Photosynthesis Reaction: Mechanism of PS-I and PS-II Reaction
❖ It absorbs light at 680 nm so the name P680.
When one photon hit P680, it goes to the excited
state and one electron is transferred to electron
transfer chain, where the electron is transported
via different electron transfer molecules. During
this transport ATP is synthesized
❖ Finally the electrons are transferred to P700
complex. P700 absorbs light at 700 nm

❖ In PS-I also the electron are transported via a

different electron transfer chain and finally
NADPH is produced from NADP+
❖ This NADPH is used to reduce CO2 in to
carbohydrates in the dark reaction. During this
reaction ATP is converted in to ADP & energy.
This energy is utilized to convert CO2 to
carbohydrate
❖ The electrons lost by P680 is compensated by the
electrons produced by splitting of water in to O2
145
and H+ as shown in the reaction
A Photosynthesis Road
Map

146
Hemoglobin Hb

Hb is not an exact Four units of

tetramer of Mb Hb

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

147
❖ 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. 148
❖ 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
149
Synthesis of Porphyrins
Porphyrins are molecules with
four pyrrole units linked by four
methine bridges having a square
planar conformation. An
unsubstituted porphyrin, known
as porphin, represents the
simplest porphyrin. Numerous
functional groups can be
substituted onto porphin
macrocycles at the meso-position
or the β-position producing a wide
variety of porphyrin derivatives. In
addition, free-base porphyrins can
be coordinated with numerous
metal ions at the porphyrin center
to form metal complexes, known
as metalloporphyrins
150
• The porphyrin macrocycle contains 18 delocalized π-electrons, that are in accord with Hückel’s rule of
aromaticity with the (4n + 2) π-electrons of the porphyrin corresponding to an aromatic system.

151
Preparation of metalloporphyrins
❖ Deprotonated, porphyrins are some
excellent tetradentate ligands. They
can be metalated by almost all the
metals from the periodic table by
reaction with the corresponding metal
salts. In biological systems, the
properties of metalloporphyrins often
depend on the nature of the
coordinated metal. Under its dianionic
form, the four electron pairs of the
nitrogen atoms are oriented toward the
center of the macrocycle. Thus, the
metal is often located at the center of
the porphyrin cavity.
❖ The minimum coordination number of the metal is equal to four but it can increase to six
thanks to the coordination in axial positions. Axial positions play a central role in the
reversible axial ligation of adducts. 152
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
153
 Hemoglobin: Tense (T) and Relaxed (R) States; Deoxy
versus Oxy: The cooperative effect
• Binding of O2 to Hb is cooperative. The presence of
bound oxygen favor addition of more O2. The Hb
molecule goes from a tense to a relaxed state. Pockets
of heme gets more easy for the following O2 units to
access due to breaking of some weak interactions.
• This happens like chain and pulley. The pulling of the
proximal histidine along with the activity of Fe getting
into the plane of the porphyrin triggers this activity

Removing the first

stamp requires more Deoxy Hb Oxy Hb Courtesy: Prof. Anil J. Elias,
effort IIT Delhi 154
Hemoglobin: An allosteric
protein
An allosteric protein does not have fixed properties. Its functional characteristics of are
regulated by specific molecule present in its environment. Hemoglobin is an allosteric protein
while Myoglobin is not.
Function of Hemoglobin in the living system is regulated by oxygen partial pressure, H+
concentration and 2, 3 biphosphoglycerate presence (BPG)

Bohr Effect (effect 2,3-BPG (saturation of

of H+ on Hb) O2 on Hb-F) 155
The Bohr Effect
Christian Bohr, father of Niels Bohr discovered this effect. An increase in concentration of
protons and/or carbon dioxide will reduce the oxygen affinity of hemoglobin

The chemical basis for the Bohr effect is due to

the formation of two salt bridges of the
quaternary structure. One of the salt bridges
is formed by the interaction between Histidine
146 and Lysine 40. This connection will help to
orient the histidine residue to also interact in
another salt bridge formation with the
negatively charged aspartate 94. The second
bridge is formed with the aid of an additional
proton on the histidine residue.
A salt bridge ( weak
Below a pH of 6, the imidazole ring of histidine electrostatic
is mostly protonated thus favoring salt bridge interaction)
formation 156
2, 3 biphospho glycerate
(BPG)
The organic compound 2, 3
biphospho glycerate
(BPG) binds to hemoglobin
A and reduces its O2 affinity
by a factor of 26. This at the
first instance will make one
wonder why? Interestingly,
this increases the oxygen-
binding affinity of fetal
hemoglobin (Hb-F) relative
to that of maternal (Hb-A)
hemoglobin. This difference
in oxygen affinity allows
oxygen to be effectively 2,3-
transferred from maternal to Biphospho
fetal red cells, the transport glycerate
of oxygen from mother to
fetus. 157
Can the prosthetic unit part of a metalloprotein perform its normal function without the protein
unit around it ?

James Collman at Stanford University succeeded in

demonstrating reversible oxygen binding to the "picket
fence" porphyrin complex shown below. The bulky tert-
butyl groups serve to keep the bound oxygen from
bridging to another complex.

• Steric hindrance: The globlin part of the molecule prevent one oxoheme from attacking
another heme. The embedded heme will reversibly bind dioxygen. And more recently, this
same result has been achieved by “picket-fence” – that reversibly binds oxygen 158
 Lighter elements are more abundant in general and therefore utilized more.

3d metals, rather than 4d, are used as catalytic centers in metalloenzymes.

❖ Why has Mo (4d) rather than Cr (3d) been utilized more biologically?
• Although Mo is rare in the earth’s crust, Mo is the most abundant transition metal in sea water as MoO4−
has fairly high solubility in water. Better correlation exists between the abundance of elements in in
human body and in sea water than between the human body and the earth's crust. Taken as evidence
for the oceans as the site of evolution of life.
❖ Despite the high abundance of Si, Al and Ti (the 2nd, 3rd and 10th most abundant elements on earth).
Why are they are not utilized biologically?
• Because of the insolubility of their naturally occurring oxides (SiO2, Al2O3, TiO2) under physiological
conditions. A lower oxidation state is unavailable for Si and Al and unstable for Ti in an aerobic
environment and is readily oxidized to Ti(IV) at pH 7.
❖ Co2+ and Zn2+ have very similar coordination chemistry and ionic size and can be interchanged in many
Zn enzymes without loss of activity. Why is Co not utilized more biologically?
• Zn is much more abundant and therefore has been utilized more.

❖ Why has cobalt been given an essential role in cobalamins despite its very low availability?.
• The unique properties of cobalt (e.g. its oxidation states, redox potentials and coordination chemistry) is
needed to achieve essential functions of B12 coenzymes 159
 Reference Books

• J.D. Lee, Concise Inorganic Chemistry, Oxford University Press, 5th Edition, 2014.
• F.A. Cotton, G. Wilkinson, C.A. Murillo and M. Bochmann. Advanced Inroganic Chemistry, 6th
Edition, John Wiley, 2007
• J.E. Huheey, E.A. Keiter, R.L.. Keiter and O.K. Medhi Inorganic Chemistry: Principles of
Structure and Reactivity, 4th Edition, Pearson Education, 2006.
• T. Overton, F. Armstron, J. Rourke and M. Weller. Inorganic Chemistry, 6th Edition, Oxford
University Press, 2015.

160
 Bibliography

• [Link]
chemistry/chapter/reactions-and-applications-of-coordination-
compounds/
• [Link]
Chem1_(Lower)/09%3A_Chemical_Bonding_and_Molecular_Structure
/9.09%3A_Bonding_in_Coordination_Complexes
• [Link]
complexes
• [Link]
• MSc - Study materials

161