Module-2:

Metal Complexes and Organometallics

Fall Semester 2022-2023

September - 2022

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 Contents…..(6 hours)
Inorganic complexes - structure, bonding and applications

Organometallics – introduction, stability, structure and applications of metal

carbonyls and ferrocene
Metals in biology: haemoglobin and chlorophyll- structure and property

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Module-2: Metal complexes and Organometallics
By
Dr. S. Arockiasamy
Fall Semester 2022-2023
September - 2022

Metal
+ Metal
Ligand complex

Platinum Gold Gold

complex complex complex
3
Inorganic Complexes
• Inorganic/coordination complex is a molecule containing one or multiple metal
centers that is bound to ligands (atoms, ions, or molecules that donate electrons to
the metal).
• These complexes can be neutral or charged. The examples are:

Neutral Complexes: [CoCl3(NH3)3], K4[Fe(CN)6], etc.

Cationic Complex : [Co(NH3)6]3+ and Anionic Complex : [CoCl4(NH3)2]−
Selected examples of metal complexes with names:

[Co(NH3)5Cl]Cl2 --- Chloropentaamminecobalt(III) chloride

[Cr(H2O)4Cl2]Cl --- Dichlorotetraaquochromium(III) chloride
K[PtCl3(NH3)] --- Potassiumtrichloroammineplatinate(II)
[PtCl2(NH3)2] --- Dichlorodiammineplatinum(II)
[Co(en)3Cl3] --- tris(ethylenediamine)cobalt(III)chloride
[Ni(PF3)4] --- tetrakis(phosphorus(III)fluoride)nickel(0) 4
 Structure and Bonding
 Double Salt: Double Salts Vs Coordination Compounds
Ferric alum
(NH4)2SO4.Fe2(SO4)3.24H2O
In water: NH4+, SO42-, Fe3+
Co-ordination Compounds
NH3 3+
3Cl– Fe(CN)2 + 4KCN Fe(CN) 2.4KCN
H3N NH3 (counter ion)
Co
H3N NH3

NH3
H
ligand
4K+ + [Fe(CN)6]4-
(coordination sphere) N M
H
H
N forms a coordinate covalent bond
to the metal
Ligands
 Molecule or ion having a lone electron pair with an atom (donor) that can be
donated to a metal atom forming a dative bond is called a Lewis base.
 coordinate covalent bond: metal-ligand bond
 monodentate : one bond to metal ion
 bidentate : two bonds to metal ion
 polydentate : more than two bonds to a metal ion possible

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Chelating Agents EDTA-Na2

• Bind to metal ions removing them

from solution.
• Phosphates are used to tie up Ca2+
and Mg2+ in hard water to prevent
them from interfering with
detergents.
EDTA-Metal complex

• Important biomolecules like heme

and chlorophyll are porphyrins
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.
Werner Coordination Theory
Werner's Theory: Alfred Werner, Swiss chemist put forward a theory to explain the
formation of complex compounds.

trans-

cis-
Limitations:
1. Bonding within coordination sphere.
2. Square planar (or) Tetrahedral
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.

It does not explain the color indicated by coordination

compounds, the thermodynamic/kinetic stabilities of
coordination complexes. Also, it does not differentiate
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Limitations between weak/strong ligands.
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 D LARGER D
to the ligand.
 (a) CN–, (b) NO2–, (c) phen,
LONGER  SHORTER  (d) en, (e) NH3, (f) gly, (g)
H2O, (h) ox2–, (i) CO3 2–

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

Tetrahedral Geometry Formation of [Cu(Cl)4]2-
Cu 1s2 2s2 2p6 3s2 3p6 3d9 4s2
Electronic configuration of Cu2+ ion

Cu2+

3d9 4s0 4p0

Change in Electronic configuration of Cu2+ ion when Cl- ligands approaches the copper ion
Cl-

Cu2+
Cl- 4p0
Cl -
3d9 4s0
Cl-  Tetrahedral and one
Electronic configuration of Cu2+ ion in Cu(Cl4)2- unpaired electrons hence
Cl- paramagnetic
Cl- Cl- Cl- Cl-  Attracted by magnets
 No. of d electrons=AN of
central metal – number of
Cu2+
Cl- Cl- electrons lost – AN of
3d9 4s2 4p6 previous inert gas (Argon -
Cl- 18) – Cu: 29-2-18 = d9
[Cu(Cl)4]2-
sp3 hybridization
Tetrahedral and
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paramagnetic
Square Planar Geometry Formation of [Ni(CN)4]2-
Ni 1s2 2s2 2p6 3s2 3p6 3d8 4s2
Electronic configuration of Ni2+ ion

Ni2+

3d8 4s0 4p0

Change in Electronic configuration of Ni2+ ion when CN- ligands approaches the nickel ion

CN- CN-
Ni2+
3d8 4s0 4p0
CN- CN-  Square planar and
diamagnetic since all
Electronic configuration of Ni2+ ion in Ni(CN4)2- electrons are paired
N-C CN- CN- CN- CN- CN-  Weekly repelled by
Ni2+ magnets
 No. of d electrons=AN of
N-C CN- central metal – number of
3d8 4s2 4p4 electrons lost – AN of
previous inert gas (Argon -
[Ni(CN)4]2- 18) – Ni: 28-2-18 = d8
dsp2 hybridization
Square planar and
diamagnetic 13
 Octahedral sp3d2 Geometry Formation of [CoF6]3-
Co 1s2 2s2 2p6 3s2 3p6 3d7 4s2
Electronic configuration of Co3+ ion
 4 No. of unpaired e-
Co 3+
ns , paramagnetic,
High spin complex
3d6 4s0 4p0 4d0  No. of d
electrons=AN of
Change in Electronic configuration of Co3+ ion when F- ligands approaches the Cobalt ion central metal –
F- number of electrons
F- F- lost – AN of
previous inert gas
Co3+ (Argon -18) – Co:
3d6 4s0 4p0 4d0 27-3-18 = d6
F- F-
F-
Electronic configuration of Co3+ ion in (CoF6)3-
F- F- F- F- F- F-
F- F-
Co3+

F- F- 3d6 4s2 4p6 4d4

F-
[CoF6]3-
sp3d2 hybridization
Octahedral geometry
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Paramagnetic in nature
15
 Octahedral d2sp3 Geometry Formation of [Fe(CN)6]3-
Fe 1s2 2s2 2p6 3s2 3p6 3d6 4s2
Electronic configuration of Fe3+ ion

Fe3+

3d5 4s0 4p0

Change in Electronic configuration of Fe3+ ion when CN- ligands approaches the Fe ion
CN-
CN- CN-
Fe3+
3d5 4s0 4p0
CN -
CN -

CN-
Electronic configuration of Fe3+ ion in [Fe(CN)6]3-  1 No. of unpaired e-
CN- CN- CN- CN- CN- CN- CN- Why? Only CFT ns , paramagnetic,
LOW spin complex
CN- CN explains this but
 No. of d
-
not VBT
Fe3+ electrons=AN of
central metal –
number of electrons
CN- CN- 3d9 4s2 4p6 lost – AN of
CN- previous inert gas
(Argon -18) – Fe:
[Fe(CN)6]3- d2sp3 hybridization 26-3-18 = d5

Octahedral 16
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.
CFT Assumptions M in presence
of L
 Interaction between the metal ion and
the ligands are purely electrostatic M in spherical
(ionic) magnetic field

 Ligands are considered as point

charges
 Ion-ion interaction, if the ligand is
negatively charged and ion-dipole
interaction, if the ligand is neutral
 Electrons on the metal are under D orbitals
when M is in
repulsion from those on the ligands  Interaction between electrons of the free state
 Electrons on metal occupy those d-
cation and those of ligands are
orbitals farthest away from the entirely repulsive. This is
direction of approach of ligands. responsible for splitting of d
orbitals.
 CFT does not consider the
overlapping between metal and
ligand orbitals.
 d-orbitals loses their degeneracy
due to the approach of ligands
during the formation of complex 18
Octahedral Complex
d-orbital – half filled
dxy = orbital lobes lie in-between x and y axis
dxz = orbital lobes lie in-between x and z axis
dyz = orbital lobes lie in-between y and z axis
dx2-y2 = orbital lobes lie along x and y axis
dz2 = orbital lobes lie along z axis and there is a
donut shape ring lie on the xy plane

 Ligands will interact with some d orbitals more

preferably than others depending on relative In these orbitals, the ligands are between the
orientation of orbital and ligand lobes, interact less strongly
Ligands are right at lobes

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Ligands and orbital LOBES dxy = orbital lobes lie in-between x and y axis
dxz = orbital lobes lie in-between x and z axis
dyz = orbital lobes lie in-between y and z axis
dx2-y2 = orbital lobes lie along x and y axis
dz2 = orbital lobes lie along z axis and there is a donut shape ring lie on the xy plane
L
L

M
M

dyz

eg t2g

dz2 = More repulsion between ligand dxy = Less repulsion between ligand and metal ion
and metal ion
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Octahedral Field Metal ion in
presence of
ligands

Metal ion in a
Spherical
negative field

 d-orbitals in the isolated gaseous metal are  If the discrete point charges (ligands) are
degenerating. allowed to interact with the metal, then the
 If a spherically symmetric field of negative degeneracy of the d orbitals is removed.
charges is placed around the metal, these  Not all d orbitals interact with the six point
orbitals remain degenerate, charges to the same extent.
 but all of them are raised in energy as a result  Those orbitals along the axes will be
of the repulsion between the negative charges destabilized more than that of the orbitals that
on the ligands and in the d orbitals. lie in between the axes.
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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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Octahedral Complex and d-Orbital Energies
 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) :
(a) Either pairing the electrons in t2g set (low spin or
strong field),
(b) Electrons in eg set, higher in energy, do not pair
(high spin or weak field).
 Pairing energy (P) and eg-t2g splitting (∆0 or 10 Dq)
(D and q are two different terms – Differential of
quanta)

Pairing energy is
needed in order to
force an electron to
fill an orbital that is
already occupied
with an electron.
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CFSE, electronic arrangements and spin only magnetic moment of Octahedral complexes

Orbital occupancy for high- and low-spin complexes of d 4 through d7 metal ions

high spin: low spin: high spin: low spin:

weak-field strong-field weak-field strong-field
ligand ligand ligand ligand

eg eg
eg eg
Δo Δo

t2g t2g
t2g t2g

eg eg
eg eg
Δo

t2g t2g
t2g
t2g
Δo < P Δo > P
[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)

Colour of Vanadium complex

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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)
Examples

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Some limitations of CFT are as follows:

• This theory only considers the d-orbitals of a central atom. The s and p
orbits are not taken into account in this study.
• The theory fails to explain the behaviour of certain metals, which exhibit
large splitting while others exhibit minor splitting. For example, the theory
provides no explanation for why H2O is a stronger ligand than OH–.
• The theory excludes the possibility of p bonding. This is a significant
disadvantage because it is found in many complexes.
• The orbits of the ligands have no significance in the theory. As a result, it
cannot explain any properties of ligand orbitals or their interactions with
metal orbitals.

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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 Metals

 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 (the Mond process).
Detection of Complex Formation
In the qualitative methods of analysis, complex formation
is of immense importance in the identification by color
change and separation of most inorganic ions.

 Formation of Precipitate
Ni2+ + 2 HDMG [Ni(DMG)2] + 2H+

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

Industrial Applications
• Coordination compounds are used as catalysts for many
industrial processes. Examples rhodium complex,
[(Ph3P)3RhCl], a Wilkinson catalyst – Catalytic hydrogenation of
alkenes. Wilkinson catalyst

Alkene Alkane

• 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(S 2O3)2]3– .
• Prussian blue – Mixture of hexacyanoFe(II) and Fe(III) -
Fe4[Fe(CN)6]3 inks, blueprinting, cosmetics, paints (commercial
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.
Organometallics – Introduction, stability, structure and
applications of metal carbonyls and ferrocene

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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.
 Discovery 1827
Zeise’s Salt- The first transition metal
organometallic compound:  Structure ~ 150 years later

K2PtCl4 + C2H5OH K[(C2H4)PtCl3]. H2O + KCl

First -bonded Organometallic Compound- Diethyl Zinc:

3 C2H5I + 3 Zn  (C2H5)2Zn + C2H5ZnI + ZnI2
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Nomenclature of Ligands
“eta-x” was originally developed to indicate how many carbons of a π-system were

η x coordinated to a metal center. Hapticity is another word used to describe the bonding
mode of a ligand to a metal center. An η 5-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.

M M M
η5-Cp η3-Cp η3-allyl η1-allyl
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Organometallic compounds are classified into three types.
• (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.
K
H Cl
• (b) Zinc compounds of the formula R2Zn such as (C2H5)2Zn H
Fe Pt Cl
(ii) Pi (π) bonded organometallic compounds: H H Cl
These are the compounds of metals with alkenes, alkynes, Cr
Zeise's salt
benzene and other ring compounds. In these complexes, the Ferrocene
metal and ligand form a bond that involves the π-electrons of Fe(5-C5H5)2
Dibenzene chromium
the ligand.
Cr(6-C6H6)2
(iii) Sigma and π-bonded organometallic compounds
Metal-carbonyl compounds formed between metal and carbon monoxide possess both σ-and π-
bonding. Generally, oxidation state of metal atoms in these compounds is zero.
O
CO CO C CO
CO OC
CO OC CO O
OC Fe Cr C
Ni CO OC Fe Fe CO
CO OC CO
OC CO
CO OC CO
CO C
O
Ni(CO)4 Fe(CO)5 Cr(CO)6 Fe2(CO)9
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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 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 of a 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.

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Example 1 

Complexes with 18 e- count are referred to as saturated.
Complexes with count lower than 18e- are called unsaturated.

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. CH3
R3P CO
Re
1) There is no overall charge on the complex PR3
2) There is one anionic ligand (CH3−, methyl group) CO

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-
this in two different ways: Re(+1), Re(I), or Re I.
Total: 18e- 42
Other examples
16 e-

16 e-

18 e-

16 e- 16 e- 43
 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 IR spectrum

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

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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.
Stretches at Stretches at lower
Stretches at still
higher frequency than
lower frequency
frequency
free -CO
than free -CO 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.
45
 Types of CO-Metal bonding interactions

Bond strength

High

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. 46
Effect of Electron Density on Metal
 As the electron density (charge) 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.

weak –C-O bond

υCO decreases because of
e- charge on metal increases
 This increases the M-CO bond strength making it more
double-bond-like, i.e., the resonance structure M=C=O
and weakens C-O bond.
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.
Example 1

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
47
on reduction.
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 48
σ/π Bridging CO

 The –CO ligand not only acts as a traditional σ-donor/π-acceptor to one or more metal
centers, but also act as a π-donor to additional metals.
 This will occur for more electron deficient 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!. Hence IR frequency further
reduced
49
Applications
2. Determination of Bond orders (BO)
 It has been seen that I.R. absorption frequency of ligated CO
1. Determination of geometries of Carbonyls
is directly proportional to its B.O.
 Calculating number of IR active bands with  In other words the I.R. absorption band due to the
Raman active bands and then tally with stretching vibration of ligated CO with a higher B.O. would
number of bands predicted theoretically 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.
E.g. 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) (resist back bonding)

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 50
3. To differentiate between terminal and bridging carbonyl groups
Bon
d stre
n gth
is wea
ken
e d

IR b
liga and for
nd brid
ged
–CO

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. And Co2(CO)8 could be used for hydrosilation of olefins.

7. In the Mond process, nickel carbonyl is used to produce pure nickel.

51
8. In organometallic chemistry, metal carbonyls serve as precursors for the preparation of other ogranometalic complexes.
Structure of Ni(CO)4

52
Applications
1. 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.
2. Fe(CO)5 is used for the preparation of inductors, pigments, as dietary supplements in the
production of radar-absorbing materials in the stealth technology, and in thermal
spraying.
3. 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 (hydroformylation).
H2 + CO + CH3CH=CH2 → CH3CH2CH2CHO

4. Several other Metal-Carbonyl complexes have been employed in the hydrocarboxylation

and hydrogenation reactions. Dicobalt octacarbonyl [Co2(CO)8] can be used for
hydrosilylation of olefins also.
5. Many organometallic complexes are the sources for the pure metal particles/ metal
coatings using Chemical Vapour Deposition (CVD) process. 53
Structure and Bonding in 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) Fe 2+
[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
54
• 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.

2. 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.

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

4. 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.
55
Ferrocene’s Applications: Ferrocene powder

 Fuel additive,
 smoke suppressant
 chiral catalyst precursor

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.

Diesel oil with ferrocene

Diesel oil with ferrocene

56
 Exhaust

Spark
Fuel Additive to reduce Knocking !!!, so what is Fuel + Air
knocking?

V2
V1

Ferrocene and its derivatives

could be used as antiknock
agents in the fuel for petrol
engines. They are safer than
previously TEL

Compression Ratio (CR)= (V1/V2) =1

V1 = Gaseous vol. in the cylinder at the end
of suction stroke
V2 = Volume at the end of compression stroke
 Ferrocene and its
derivatives could be
Exhaust used as antiknock

Spark
Exhaust Fuel + Air agents in the fuel for

Spark
Fuel + Air
petrol engines. They are
safer than previously
TEL

V2
V2
V1
V1

SUCTION Knocking in petrol engines are

COMPRESSION due to pre-ignition.
Knocking increases V2, reduces
Compression Ratio (CR)= (V1/V2) VI, Hence Compression ratio
~1 falls below subsequently
V1 = Gaseous vol. in the cylinder at the end of suction stroke efficiency of the engine
V2 = Volume at the end of compression stroke decreases.
 Metals in biology

Contents……Metals in biology (haemoglobin, chlorophyll-

structure and property)
59
Chlorophyll- Structure and Property R

 Structure of Chlorophyll H 3C
• Chlorophylls are green pigments with polycyclic, planar N N
structures resembling the protoporphyrin system present Chlorophyll Mg
in haemoglobin N N
• In chlorophyll, Mg2+ is the metal centre H 3C CH3
• The four inward-oriented nitrogen atoms of the porphyrin
ring in chlorophyll are coordinated with the Mg2+ O
• All chlorophylls have a long phytol side chain, esterified O O H3C-OOC
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
photosynthesis 60
 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.

61
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

62
Photosynthesis Reaction
Nicotinamide Adenine
Dinucleotide Phosphate
Hydrogen (NADPH)

Two types of photosystems

cooperate in the light reactions 63
A Photosynthesis Road Map

Nicotinamide Adenine Dinucleotide

Phosphate Hydrogen (NADPH)
Adenosine 5'-triphosphate (ATP)

64
Hemoglobin Hb  141 Amino acid
 146 Amino acid
Mb 153 Amino acid

Hb is not an exact Four units of Hb

tetramer of Mb

CH3

H 3C 3 major types of Hb
N N Hb A (Adult)
Fe
Hb F (Fetal)
N N
H 3C CH3 Hb S (Sickle cell)

COOH COOH

65
 Each of these subunit polypeptides contains a heme
group—an iron atom at the center of a poryphyrin ring CO2
—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 Fe 2+

heme iron, which is why the color of blood changes
from the dark, purplish hue characteristic of venous
66
blood to the brilliant scarlet of arterial blood.
 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
two 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
67
 deoxy-hemoglobin oxy-hemoglobin
 Role of distal H2C CH3 O
H2C O CH3
histidine: Makes O2 H3C
N N CH2 H3C
O2 N N CH2
to bind in a bent N Fe2+ N 3+
Fe
H3C CH3 N N
fashion and makes it H3C CH3
N
difficult for CO to bind -
OOC COO-
-
OOC
N COO-
in a linear fashion. HN
HN

 An isolated heme peptide

peptide
chain
binds CO 25000 times chain

as strongly as O2 in
Distal
solution. In the living N histidine
N

system binding affinity H

N
N
H
Protein
H N
N
Protein
H
for oxygen is reduced N
N Fe
N
N Fe O

considerably. For CO N N O

to bind strongly, it has

Protein
Protein
Proximal Tense (T) state Relaxed (R) state
to bind linearly which histidine

is made difficult by Fe2+ t2g4eg2, HIgh spin, radius 92 pm Fe3+ t2g5eg0, Low spin, radius 75 pm

distal histidine Paramagnetic Diamagnetic

Fe 42 pm outside porphyrin plane Fe fits inside the porphyrin plane 68