Inorganic Spectros

Organometallics, Non-Metals and Inorganic Spectroscopy
MSCM202R01
Dr. D. Suresh
Department of Chemistry
School of Chemical and Biotechnology
SASTRA Deemed University
Thanjavur
E-mail Id: sureshvnr@gmail.com

Contact no.:88703 58876
suresh_d@scbt.sastra.edu
Dr. D. Suresh
sureshvnr@gmail.com
88703 58876
Cabin: ASK II, Lab number 403, Third floor
Lectures:
Day Time Class room
Monday 14:00 – 15:00 JVC 415
Tuesday 08:45 – 09:45 JVC 415
Thursday 15:15 – 16:15 JVC 415
Friday 11:00 – 12:00 JVC 415
Assessment:
Internal: 40 (CIA exams)
10 (3 class test/Quiz)
(No assignment)
End semester exam: 50
Total: 100
Dr. D. Suresh
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திருக்குறள்
பால்: அறத்துப்பால் அதிகாரம்: தீவினையச்சம் குறள்: 202
தீயவை தீய பயத்தலால் தீயவை
தீயினும் அஞ்சப் படும்.
- திருவள்ளுவர்
விளக்கம்:
• நமக்கு நன்வம என்று பிறருக்குச் சசய்யும் தீவமகள், நமக்குத்
தீவமயய தருைதால், தீவமகவைத் தீயினும் சகாடியனைாக
எண்ணிச் சசய்ய அஞ்ச யைண்டும்.
Translation:
• Since evils new from evils ever grow,

• Evil than fire works out more dreaded woe.
Dr. D. Suresh
Explanation:
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• Because evil produces evil, therefore should evil be feared more than fire.
3
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Unit IV
Physical Methods in Inorganic Chemistry

Electronic spectra of Coordination complexes: Beer-Lampert law – Term
symbols – Selection rules – Octahedral complexes: Orgel and Tanabe–Sugano
diagram – Jahn–Teller Distortions – Calculation of Dq, , Nephelauxetic ratio.
Tetrahedral complexes: Charge transfer (LMCT, MLCT) – CT Applications.
IR and Raman spectroscopy: Vibrational modes – Group frequencies of infrared

systems – Factors affecting the group frequencies – IR spectra of coordination
compounds. Changes in ligand vibration on coordination with metal ions.
Vibrational spectra of metal carbonyls.
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Unit IV
Nuclear spectroscopy: The contact and pseudocontact shifts – Factors affecting
nuclear relaxation – Nuclear magnetic resonance (10,11B, 19F, 31P, NMR);
Nuclear quadrupole resonance.
ESR spectra of metal complexes: Hyperfine splitting and A parameter – g

values, –Zero field splitting and Kramers degeneracy. Application to Cu(II)
complexes and inorganic free radicals such as PH4, F2- and [BH3]-.
Mossbauer Spectroscopy: Basic Principles – Spectral parameters and

spectrum display. Application of the technique to the studies of iron and tin
complexes.
Spectroscopic methods for optically active complexes: Optical rotatory

Dr. D. Suresh
dispersion (ORD) – Positive and negative cotton effect – Circular dichroism
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Reference Books for Unit IV
S. F. A. Kettle
Dr. D. Suresh R. S. Drago

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88703 58876 Rankin – Mitzel – Morrison
Spectroscopy
• Spectroscopy is a general term for the science that deals with the
interactions of various types of radiation with matter.
• Exactly how the radiation interacts with matter is directly dependent on the
energy of the radiation.
Dr. D. Suresh
• The most widely used spectrometric methods are based on electromagnetic
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radiation.
Application of Spectroscopy
1. Provide information on the energy level of structure of atoms and
molecules and for understanding the molecular structure.
2. They also provides useful in analytical aspects for qualitative and
quantitative analyses.
Electromagnetic Radiation and its Interactions with Matter

• Electromagnetic radiations are the radiations consisting of waves of energy
associated with electric field and magnetic field which act perpendicular to
each other and also perpendicular to the direction of propagation of waves.
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Parameters used to EMR
Wavelength ( (lambda)):
• The distance between adjacent crest or adjacent troughs is called
wavelength. Unit of wavelength : cm, mm , mm, μm, nm , Å
Frequency ( (nu)):
• The number of waves passing through a given point in one second is called
frequency. Unit of frequency: Hz, KHz, MHz, Fresnel
Wave number ( (nu bar)):
• Number of waves per cm or m in vacuum. Unit is cm-1, m-1
Amplitude (A):
• The maximum extent of a vibration or oscillation, measured from the position
of equilibrium. Unit of amplitude: (N/m2)
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Parameters used to EMR
• The wavelength and frequency are related by the expression
• The wavelength, frequency and waver number are related by the expression
C = velocity of light in vacuum (3  108 m sec-1)

 = frequency
 = wavelength
= waver number
• The EMR is a form of energy and the energy of unit in radiation is called the
photon which is related to the frequency or wavelength given by the
Einstein-Planck relationship
E = h = hc/ = hc
Dr. D. As frequency () increases, energy (E) of light increases

Suresh
As wavenumber ( ) increases, energy (E) of light increases
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As wavelength () increases, energy (E) of light decreases
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Electromagnetic Spectrum
“பார்ப்பது கண் அளவு”
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Electromagnetic Spectrum
• X-rays, gamma rays cause the ionization of atoms/molecules and hence

referred as ionizing radiation.
• Dr. D.
Other Suresh
EMR do not so this phenomenon and are referred as non-ionizing
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radiation.
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Types of Chemical Interaction
• The nature of all these radiations is the same and all moves with the velocity
of light.
• However due to their different energies, they interact with matter very
differently.
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Types of Chemical Interaction
EMR Regions Changes in atom/molecule Techniques and instrumentation
-rays -ray spectroscopy
Nuclear Configuration
0.05 – 1.4 Å -ray spectrometer
X-rays Core electron distribution X-ray absorption spectroscopy
0.1 – 100 Å in atoms X-ray spectrometer
Valence shell electron Electronic absorption spectroscopy
UV-Visible
transition in atoms and UV-Visible spectrometer
190 – 780 nm Atomic absorption spectrometer
molecules
Vibrational spectroscopy
Infrared Vibrational transition in
Infrared spectrometer
0.8 – 200 m molecules Raman spectrometer
Microwave Rotational characteristics Rotational spectroscopy
0.75 – 3.75 m of molecules Microwave spectrometer
Magnetic resonance spectroscopy
Nuclear and electron spin
Radiofrequency Nuclear Magnetic Resonance
in presence of external
3 cm – 10 m (NMR) and Electron Spin
Dr. D. Suresh magnetic field Resonance (ESR) spectrometer
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Over view of Energy Levels Matter (Molecules/Atoms)
• The total energy of molecule is due to contributions from different sources.
• This includes the
1. Nuclear energy - Energy due to spinning motion of nucleus and
electrons
2. Electronic energy - Due to interactions between electrons and
nuclei
3. Vibration energy – Due to vibration motion of molecules
4. Rotation energy - Due to rotation motion of molecules
5. Translation energy – Due to movement in air
Etot = Eelec + Evib + Erot + Espin + Etrans + Enuc
• Dr.
All theD. Suresh
forms of energy levels are quantized, except the translational energy.
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Energy Levels in Atoms
• The energy structure of atom is simpler and consists of only the electronic
energy levels usually designated as S0 the ground state (the lower energy
level) and S1, S2, S3,....etc. for the excited states having higher energies.
• The occupancy of the electronic S3
Energy
energy levels in atoms under ambient
S2
conditions is determined by Quantum
theory and Maxewell-Boltzman S1
distribution equation
S0
Dr.
N1 =D. Suresh in ground state; E1 = energy of ground state
population
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N2 = population in excited state; E2 = energy of excited state
88703 58876constant 1.3806  10-23 JK-1
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K = Boltzmann
Interaction of EMR with atoms
• The interaction between EMR with atoms may involve transfer energy of
incident photons to that atoms which raises their energy from ground state to
an excited state. • Absorption occurs only when the energy
difference between the any two level is
exactly matches with the energy of
S3
incident radiation. E = h
non-radiative
process • Excited atoms are stable only for very
short time (10-9 s) and relax to the ground
S2 state either by radiative or non-radiative
process.
non-radiative
Energy
Absorption process • In non-radiative process, the energy is

converted into translation energy and
S1
emits as heat radiation.
Fluorescence • Radiative relaxation process is called
Dr. D. Suresh fluorescence. Occurs only from S1 to S0
sureshvnr@gmail.com S0 • Absorption  or  = Fluorescence  or .
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Resonance Fluorescence.
Energy Levels in Molecules
• Unlike the energy structure of atom, the energy level of molecule consists of
electronic energy levels (S) which in turn contains several sub levels like
vibrational levels (v), rotational energy levels (j).
The relative magnitude energy levels are in the order of

Eelec > Evib > Erot > Enuc.spin
S2
electronic energy levels (S)

Energy
S1 v3 vibrational energy levels (v),

rotational energy levels (j)
v2
Dr. D. Suresh j3
j2
v1
sureshvnr@gmail.com j1
S0
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Energy Levels in Molecules
LUMO
HOMO
Energy
LUMO h LUMO
Excited state Singlet HOMO
HOMO
Ground state Excited state Triplet

Singlet
Energy of Excited state Singlet > Energy Excited state Triplet
For free radical, containing unpaired electrons...!
LUMO LUMO
or
HOMO HOMO
Dr. D. Suresh Ground state

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Ground state
Doublet
Doublet
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Interaction of EMR with Molecules
• When the absorb energy in the form of UV and Visible region, the valence
shell electrons are get promoted to higher energy levels.
• These transition give rise to a spectrum are called Electronic absorption
spectroscopy or absorption spectroscopy
• Energy involved in electronic transitions are around 400 KJ mol-1.
• When molecules absorb energy in the infra red region the vibrational
transition occurs. These transition give rise to a spectrum are called
Vibrational spectroscopy or IR spectroscopy.
• When molecules absorb energy in the microwave region the rotational

transition occurs. These transition give rise to a spectrum are called
Dr. D. Suresh
Microwave spectroscopy.
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• Energy involved in electronic transitions are around 0.4 KJ mol-1.
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Interaction of EMR with Molecules
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UV-Visible Absorption Spectroscopy
• Molecules absorb energy in the form of UV and Visible region in which the
valence shell electrons are get promoted to higher energy levels.
• These transition give rise to a spectrum are called Electronic absorption
spectroscopy or absorption spectroscopy
• The excited state molecules relaxed to ground state by emitting either
fluorescence or phosphorescence in the UV-Visible region.
• The emitted radiation is analyzed by the spectrophotometer and the
graphical plot of intensity of emission as a function of frequency or
wavelength is appropriated called as fluorescence or phosphorescence

Dr. D. Suresh
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emission spectrum.
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UV-Visible Absorption Spectroscopy
Jablonski Diagram: Absorption or Exicitation (10-15 s)
Vibrational and rotational relaxation

S2 due to collisions between the molecules
of the excited species and those of the
IC (10-14 to 10-10 s) solvent (non-radiative process)
Internal conversion (IC) when two
S1 levels are sufficiently close energetically.
(non-radiative process)
Fluorescence
ISC
(10-10 to 10-8 s) T1
Energy
IC
(10 to 10-10 s)
-14
Intersystem crossing (ISC) (reversal of

spin), common in molecules containing
heavy atoms or when paramagnetic species
are present (non-radiative process)
S0 Vibrational and rotational
levels
Dr. D. Suresh
Fluorescence always from lowest vibrational Phosphorescence always from lowest
level of an excited electronic singlet state vibrational level of an excited electronic triplet
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(radiative process) (10-9 to 10-6 s) state (radiative process) (10-3 to 100023s)
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Typical Absorption spectrum
Absmax
Absorption
• Both rotational and vibrational modes are found combined with electronic
transitions and hence the absorption peaks are broader.
• The intensity () of UV-Vis spectroscopy is having very large magnitude in

Dr.order
the D. Suresh
of 10,000 and hence the dilute solutions are more easily measured
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in UV-Vis Spectroscopy.
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Fundamental Laws of Photometry
Lambert’s Law:
• States that absorbance of a material sample is directly proportional to its
thickness (path length).
I0 = intensity of incident light
It = intensity of transmitted light
It = I0  10kl k = proportionality constant
l = thickness or path length
I0 It It
I0 I0
l
Beer’s Law:
• States that absorbance is proportional to the concentrations of the analyte
It = I0  10k’c I0 l
IT
I0 = intensity of incident light h
Dr.
It D. Suresh
= intensity of transmitted light
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K’ = proportionality constant Absorbing medium
(solution of concentration c)
c = concentration
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Fundamental Laws of Photometry
Beer-Lambert’s Law:
• States that absorbance is proportional to the concentrations of the analyte
and the thickness or path length
I0 = intensity of incident light
 Io 
It = I0  10cl log   εCl It = intensity of transmitted light
 IT   = molar absorption coefficient
 Io  l = thickness or path length
log   εCl  A  Optical Density A = Absorbance or Optical density
 IT 
Transmittance (T):
• The ratio of It/I0 is the transmittance T of the medium i.e the fraction of
incident light transmitted by the medium.
• Usually expressed as percentage T (%T)
I0 = intensity of incident light;
• Absorbance and Transmittance are related as It = intensity of transmitted light;
 = molar absorption coefficient;
Dr.
Io  D. Suresh  1 l = thickness or path length;
log   εCl  A  Optical Density  log 
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 IT  T
A = Absorbance or Optical density;
T = Transmittance
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Application of Beer-Lambert’s law
1. For qualitative and quantitative analyses.
2. To find the percentage purity of the analyte.
• For qualitative analysis the value of  is significant and its magnitude is
affected by,
• Wavelength of incident radiation
• Chemical nature of absorbing molecule
Quantitative analyses
Unknown sample
Dr. D. Suresh
sureshvnr@gmail.com OD of unknown × Conc. of a standard
Concentration of unknown solution =
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OD of the standard
Limitation of Beer-Lambert’s law
Limitation of Beer–Lambert law:
• Beer–Lambert law is capable of describing absorption behaviour of solutions
containing relatively low amounts of solutes dissolved in it (<10 mM).
• When the concentration of the analyte in the solution is high (>10 mM), the
analyte begins to behave differently due to interactions with the solvent and
other solute molecules and at times even due to hydrogen bonding
interactions.
Deviations from Beer–Lambert law:
• Beer–Lambert law fails to maintain a linear relationship between dilution and

concentration of analyte, under certain conditions.
• These deviations are classified into three categories,
• Real deviations
Dr. D. Suresh • Chemical deviations
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• Instrument deviations
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Deviations from Beer–Lambert law
Real Deviations:
• Due to the limitation of the law itself.
• At higher concentration, the refractive index of the solution is changed which
is directly related to the molar absorptivity ().
• High concentration may also lead to aggregation.
• Large aggregates then scatter light.
• The intensity of the radiation reaching the detector is thus lessened.
• Thus two different phenomena are contributing to the reduction in the
transmitted intensity - absorption and scattering.
• In such a case a there will be a deviation.
• Over an extremely small concentration range known as the critical micelle

concentration (cmc).
Dr. D. Suresh
• Certain kinds of solute molecules cooperatively associate into large
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58876
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particles, micelles.
Deviations from Beer–Lambert law
Real Deviations:
• The micelles are huge particles by comparison since each micelle may
contain more than 100 molecules per particle.The micelles cause
appreciable scattering of radiation in the X-ray to visible region.
Chemical Deviations:
• These are deviations observed due to specific chemical species of the
sample which is being analysed. For example, Cr2O72- on dilution undergo
hydrolysis to give rise to another species CrO42-.
• Turbid solutions always end up giving higher absorbance than what is
determined by the color.
Instrument Deviations:
(i) imperfect monochromic; (ii) stray radiation reaching the detector; (iii)
Dr. D.changes
sensitivity Sureshin the detector; (iv) power fluctuations of the radiation
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source and detector amplification system.
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CSIR December 2014
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பால்: அறத்துப்பால் அதிகாரம்: ஊழ் குறள்: 376
பரியினும் ஆகாைாம் பாலல்ல உய்த்துச்
சசாரியினும் யபாகா தம
• தனக்கு உரிவமயல்லாதைற்வற எவ்ைைவுதான் பாதுகாப்பாக
வைத்தாலும் அவை தங்காமல் யபாய்விடக் கூடும்;
உரிவமயுள்ைைற்வற எங்யக சகாண்டு யபாய்ப் யபாட்டாலும்
அவை எங்கும் யபாகமாட்டா.
Translation:
• Things not your own will yield no good, howe'er you guard with pain;
• Your own, howe'er you scatter them abroad, will yours remain.
Explanation:
• Whatever is not conferred by fate cannot be preserved although it be
Dr. D. Suresh
guarded with most painful care; and that, which fate has made his, cannot
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be88703 58876one should even take it and throw it away.
lost, although
Recalling Previous Lecture…!
Beer-Lambert’s Law:
 Io   1
log   εCl  A  Optical Density  log 
 IT  T
Unknown sample
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Electronic configuration and Quantum numbers
Principal quantum number (n) Angular quantum number (l)

describes the size and energy 2s2 2p2 describes the shape of the
of the orbital orbital
n = 1,2,3,4… l = 0, 1, 2, 3, 4…,(n−1)
l = s, p, d, f, g…
Magnetic quantum Number (ml),
determines the number of orbitals and
their orientation within a subshell
ml =+l to 0 to -l
ml value 0
s-orbital l = 0 Electron spin quantum number (ms)
It designates the direction of the
electron spin and may have a spin of
ml value +1 0 -1 +1/2 () or -1/2 ()
p-orbital l = 1
Does not depend on another
quantum number.
ml value +2 +1 0 -1 -2
d-orbital l = 2
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ml value +3 +2 +1 0 -1 -2 -3
88703 58876 d-orbital l = 3 34
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Some definition:
Term
• Energy level of an atom described by the electronic configuration is called as
Term.
• It is assumed that there is no inter electronic repulsion between the electrons
present in the same orbital.
• But the electrons in the same orbitals do experiences inter electronic
repulsion and spin-orbit coupling
Spin-orbit coupling
State describes a weak
magnetic interaction,
• Splitting of terms due to spin-orbit or coupling, of the
particle spin and
coupling is referred as State. the orbital motion of
this particle
Microstate
• Dr.arrangement
The D. Suresh of electrons in a set of orbitals has a slightly different
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energy and it is called as microstates.
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Term Symbols for Atoms
Term symbol
• Term symbols are a shorthand method used to describe the energy, angular
momentum, and spin multiplicity of an atom in any particular state.
• The term symbol for particular atomic state is given by,
S= total spin angular momentum

spin multiplicity 2S+1 LJ total angular momentum
Represented with number represented with number
The interaction between L (orbital)
total orbital angular momentum
and S (spin) is known as LS coupling
(represented with letter)
or Russell-Saunders coupling.
• The ground state term symbol can be derived in three steps,
Step 1: To calculate spin multiplicity (2S + 1)

Dr. D. Suresh
Step 2: To calculate L
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Step 3: To calculate J
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Example 1: d1 configuration,
ml value +2 +1 0 -1 -2

Step 1: To calculate spin multiplicity
spin (small “s”) of the electron is +1/2 () or -1/2 ()
number of unpaired electrons

S=
2
In this case, only one electron so both s and S = 1/2
Dr. D. Suresh
The spin multiplicity is given by, 2S + 1
sureshvnr@gmail.com 2S + 1 = 2(1/2) + 1 = 2
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L = mli (summation of magnetic quantum number of electrons)
• L can have value of zero or any positive number.
• Based on the number, select the alphabet
L = ml 0 1 2 3 4 5 ……
State S P D F G H …….
In this case, d1 configuration
Azimuthal quantum number (l) can have value from +l to 0 to -l

For, d, the l is 2, so the value is from +2 to -2
ml value +2 +1 0 -1 -2

Dr. D. Suresh
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L = (+2  1) = 2 L = 2 = D
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J = L – S when the subshell is less than half filled

J = L + S when the subshell is more than half filled
J = S when the subshell is half-filled
In this case (d1), less than half filled,

so, J = L – S
J = L – S = 2 - 1/2 = 3/2
So the ground state term symbol is 2D3/2
Dr. D. Suresh
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Example 2: d9 configuration,
ml value +2 +1 0 -1 -2
    

S=
2
S = 1/2

Dr. D. Suresh  2S + 1 = 2(1/2) + 1 = 2
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L = ml 0 1 2 3 4 5 ……
In this case,
ml value +2 +1 0 -1 -2
    
L = (+2  2) + (+1  2) + (0  2) + (-1  2) + (-2  1)

= 4 + 2 + 0 -2 -2
=2
Dr. D. LSuresh
=2=D
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In this case (d9), more than half filled,

so, J = L + S
J = L + S = 3 + 1/2 = 5/2
So the ground state term symbol is 2D5/2
Dr. D. Suresh
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Example 3: p2 configuration,
ml value +1 0 -1
 


S=
2
2
S= =1
2

Dr. D. Suresh  2(1) + 1 = 3
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L = ml 0 1 2 3 4 5 ……
In this case,
ml value +1 0 -1
 
L = (+1 1) + (0  1)
=1+0
Dr. D. Suresh =1
L=1=P
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In this case (p2), less than half filled,

so, J = L – S
L–S=1-1=0
So the ground state term symbol is 3P0
Derive term symbol for fluorine atom?
Dr. D. Suresh 2P
3/2
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Term symbols for pn configurations:
Term symbols for dn configurations:
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Terms symbol for excited state atom
Number of microstates:
• The arrangement of electrons in a set of orbitals has a slightly different
energy and it is called as microstates.
• The total number of microstates (N) for an electronic configuration is given
by,
(2y)! x = number of electrons

N y = number of subshell
x! (2y - x)! ! = Factorial
• For, p2 configuration,
mL 2 0 -2 1 0 -1 1 0 -1 1 0 -1 1 0 -1
+1         
0         
1         
Dr. D. Suresh
mS 0
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01 0 1 1 0 0 0 -1 -1 -1 0 0 0
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48
Number of microstates:
by,
x = number of electrons;
(2y)!
• For p2,
(2  3)! 6! 1 2  3  4  5  6
N   = 15 micro states
2! (2  3 - 2)! 2! 4! (1  2)  (1  2  3  4)
Orbital s p d f g
Number of subshell 1 3 5 7 9
Number of subshell = 2l + 1
l – azimuthal quantum number
Calculate for p3, p4, d3, d5 and d8.
Dr. D. Electronic
Suresh configuration p3 p4 d3 d8 d5
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Number of microstates 20 15 120 45 252
88703 58876
49
பால்: பபாருட்பால் அதிகாரம்: வினைத்திட்பம் குறள்: 666
எண்ணிய எண்ணியாங்கு எய்து எண்ணியார்
திண்ணியர் ஆகப் சபறின்
• எண்ணியவதச் சசயல்படுத்துைதில் உறுதி உவடயைர்கைாக
இருந்தால் அைர்கள் எண்ணியைாயற சைற்றி சபறுைார்கள்.
Translation:
• Whate'er men think, ev'n as they think, may men obtain,
• If those who think can steadfastness of will retain.
Explanation:
• If Dr. D.who
those Suresh
have planned (an undertaking) possess firmness (in executing
sureshvnr@gmail.com
it) they will obtain what they have desired even as they have desired it.50
88703 58876
Term symbols:
2S+1L
J

by,
(2y)! x = number of electrons;
Dr. D. Electronic
Suresh configuration p3 p4 d3 d8 d5
sureshvnr@gmail.com
Number of microstates 20 15 120 45 252
88703 58876
Deriving Terms symbol for excited state atom:
+1 0 -1 mL mS
• For p2,
  +1 +1
(2y)! x = number of electrons
  0 +1
x! (2y - x)! ! = Factorial   -1 +1
 
+1 -1
(2  3)! 6! 1 2  3  4  5  6  
N   0 -1
2! (2  3 - 2)! 2! 4! (1  2)  (1  2  3  4)  
-1 -1
= 15 micro states  +2 0
 0 0
 -2 0
• For, p2 configuration, the following are 

+1 0

the electron arrangement in their  0 0

excited state in p-orbitals. (Hund’s rule  -1 0

 +1 0
Dr.applicable
not D. Suresh for excited states but 
 0 0
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Pauling’s rule should be followed) 
 -1 0
88703 58876 52
• For p2, mL mS
+1 +1
0 +1
-1 +1 mS
1 0 -1
+1 -1 mL
0 -1 +2 
-1 -1 +1   
+2 0 0   
0 0
1   
-2 0
2 
+1 0
0 0
-1 0 • Note that this form of the microstate
table will always be symmetric
Dr. D. Suresh
+1 0
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0 0 about its center.
88703 58876
-1 0
mS
• For p2, 1 0 -1
mL
• To derive term symbol choose the maximum +2 
value of mL and find the corresponding mS +1   
• mL = 2; mS = 0 0   
2S+1 LJ 1   
2 
• mL = 2 = L = D
L = ml 0 1 2 3 4 5 ……
• mS = 0 = S
2(0)+1D
= 1D
• The number of degeneracy of a term is given by the equation,
(2L + 1)(2S + 1)
Dr. D. Suresh
(2(2) + 1)(2(0) + 1) = 5
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88703 58876 1D term have 5 degeneracy level
• For p2,
• 1D term have 5 degeneracy level.
• To derive the other term symbol, it is necessary to remove the 5
degenerated level.
• Since it is a D term and has L value of 2 which has value ranges from +2,
+1, 0, -1 and -2.
• Remove one each from L value.
mS mS
1 0 -1 5 degeneracy of 1 0 -1
mL 1D term is removed mL
+2  The five degeneracy
+2
+1    microstates are +1   
chosen in such a   
0    manner that the
0
1Dr.
D. Suresh
  center of symmetry 1   
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2 
in the table will be 2
88703 58876 preserved.
• For p2, mS
1 0 -1
• To derive term symbol choose the maximum mL
+2
value of mL and find the corresponding mS
+1   
• mL = 1; mS = 1 0   
2S+1 1   
LJ
2
• mL = 1 = L = P
L = ml 0 1 2 3 4 5 ……
• mS = 1 = S
2(1)+1P
= 3P
(2L + 1)(2S + 1)
Dr. D. Suresh
sureshvnr@gmail.com (2(1) + 1)(2(1) + 1) = 9
88703 58876 3P term have 9 degeneracy level
• For p2,
• 3P term have 9 degeneracy level.
degenerated level.
• Since it is a P term and has L value of 1 which has value ranges from +1, 0,
and -1.
• Remove one each from L values.
mS 9 degeneracy of mS
1 0 -1 1 0 -1
mL 3P term is removed mL
+2 The nine degeneracy +2
microstates are
+1    chosen in such a +1
0    manner that the 0 
Dr. D. Suresh center of symmetry
1    1
sureshvnr@gmail.com in the table will be
2 2
88703 58876 preserved.
mS
• For p2, 1 0 -1
mL
• To derive term symbol choose the maximum +2
value of mL and find the corresponding mS +1
• mL = 0; mS = 0 0 
1
2S+1 LJ 2
• mL = 0 = L = S
L = ml 0 1 2 3 4 5 ……
• mS = 0 = S State S P D F G H …….
2(0)+1S
= 1S
(2L + 1)(2S + 1)
Dr. D. Suresh
(2(0) + 1)(2(0) + 1) = 1
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88703 58876 S term have 1 degeneracy level
1
• For p2,
• 1S term have 1 degeneracy level.
degenerated level.
• Since it is a S term and has L value of 0 which has value of 0.
• Remove one each from L values
mS mS
1 0 -1 1 0 -1
mL mL
+2 1 degeneracy of +2
1S term is removed
+1 +1
0  0
1 1
2Dr.
D. Suresh 2
sureshvnr@gmail.com
• For p2, configuration three terms 1D, 3P and 1S are available.
88703 58876
• For p2,
• To calculate the J value for the terms, 1D, 3P, 1S.
J = (L + S), (L+ S – 1),…..L – S 
For 1D, L= 2 and S= 0 For 3P, L= 1 and S= 1

• It’s a singlet multiplicity, hence J • It’s a triplet multiplicity, hence J can
can have only one value have three values
J = (L + S) J = (L + S), (L+ S – 1),L – S 
J = (2 + 0) = 2 J = (1 + 1), (1 + 1 – 1), (1 – 1) = 2, 1, 0
The term is 1D2 The terms are 3P2, 3P1 and 3P0
• For 1S, L= 0 and S= 0
• It’s a singlet multiplicity, hence J can have only one value
Dr. D. Suresh
J = (L + S) J = (0 + 0) = 0 The term is 1S0
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1D , 3P , 3P 3P , 1S
88703 58876 0 0 1, 2 0
Energy of the terms:
1. The term with the highest spin multiplicity (2S+1) has the lowest energy.
2. If two or more terms have the same multiplicity (e.g. 3F and 3P), the term
having the highest value of L has the lowest energy (e.g. 3F is lower than
3P).
3. For terms having the same multiplicity and the same values of L (e.g. 3P0
and 3P1), then
3a. the level with the lowest value of J is the lower in energy if the sub-
level is less than half-filled (e.g. p2),
3b. the level with the highest value of J is the lower in energy if the sub-
level is more than half-filled (e.g. p4).
Dr. the
3c. D. level
Sureshwith the maximum spin multiplicity is the lower in energy if the
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sub-level is half-filled (e.g. p3).
88703 58876
61
Energy of the terms: number of
• For p2 system, among the terms 1D, 3P, 1S. Term Degeneracy
(2L+1)(2S+1)
1D 5
ground
state
3P (highest spin multiplicity value; lower energy) 3P 9

 1S 1
1D (Lowest spin multiplicity value and highest L value; high energy)

excited
state
1S (Lowest spin multiplicity value and Lowest L value; highest energy)
• Among 3P there are 3P0, 3P1, 3P2.
Energy
• The energy levels are 3P0 < 3P1 < 3P2
Dr. D. Suresh
sureshvnr@gmail.com
88703 58876
62
LS coupling
Energy of the terms:
• Arrange the following in the increasing order of energy for the following
terms, 3F, 1D, 1S, 3P, 1G.
• By multiplicity, the order is 3F, 3P 1D 1S 1G
• Then arrange according to L value, 3F 3P 1G 1D 1S
• So the order is 3F < 3P < 1G < 1D < 1S
Dr. D. Suresh
sureshvnr@gmail.com
88703 58876
• For, d2 configuration,
mL 4 2 0 -2 -4 3 2 1 0 1 0 -1 -1 -2 -3 3 2 1 0 1 0 -1 -1 -2 -3
+2         
+1         
0         
1         
2         
mL 0 0 0 0 0 1 1 1 1 1 1 1 1 1 1 0 0 0 0 0 0 0 0 0 0
mL 3 2 1 0 1 0 -1 -1 -2 -3 3 2 1 0 1 0 -1 -1 -2 -3
+2        
+1        
0        
1        
2        
mL -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 0 0 0 0 0 0 0 0 0 0
• For, d2 configuration, the following are the electron

Dr. D. Suresh
arrangement in their excited state in p-orbitals. (Hund’s rule
sureshvnr@gmail.com
not applicable for excited states)
88703 58876
Terms symbol for excited state atom number of
For, d2 configuration,
Term Degeneracy
• By following the rules, the d2 configuration have the (2L+1)(2S+1)
terms of 1G, 3F, 1D, 3P and 1S 1G 9
3F 21
• Their corresponding degeneracy levels are 9, 21, 5,
1D 5
9 and 1, respectively (total = 45). 3P 9
• The order energy is given by, 1S 1
3F < 3P < 1G < 1D < 1S
ground
state excited state
Energy
• The energy difference between levels can be
less than or equal to the splitting of states.
• Therefore, the only configuration are certain
ofDr. D.ground
is the Sureshstate.
sureshvnr@gmail.com
• The actual order is give at the far right.
88703 58876 LS coupling
Term symbols for common electron configurations:
electron
configurations ground-state excited-state
• For each entry, the ground-state term symbol is listed first.

• Those with higher spin multiplicity and higher L value have lower energy, the
Dr. D. Suresh
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ground state.
88703 58876
66
HCU, 2016
HCU, 2015
CSIR June 2016 GATE 2007
GATE 2014
CSIR December 2014 9
CSIR July 2012

Dr. D. Suresh
sureshvnr@gmail.com
88703 58876
பால்: பபாருட்பால் அதிகாரம்: இடுக்கணழியானை குறள்: 630
இன்னாவம இன்பம் எனக்சகாளின் ஆகுந்தன்
ஒன்னார் விவையுஞ் சிறப்பு
• ஒருைன் சசயல் சசய்யும்யபாது துன்பம் ைந்தால் மனம் தைராமல்
அவதயய இன்பம் எனக் சகாள்ைான் என்றால், பவகைராலும்
மதிக்கப்படும் சிறப்பு அைனுக்கு உண்டாகும்.
Translation:
• Who pain as pleasure takes, he shall acquire
• The bliss to which his foes in vain aspire.
Explanation:
• Dr.elevation,
The D. Suresh which even his enemies will esteem, will be gained by him,
sureshvnr@gmail.com
who regards pain as pleasure. 68
88703 58876
• To derive term symbol

choose the maximum
value of mL and find
the corresponding mS
2S+1 L
Dr. D. Suresh
J having the highest value of L has the lowest energy
sureshvnr@gmail.comhighest value of L has the lowest energy
88703 58876
(2L + 1)(2S + 1)
Electronic Spectra of Complexes
• The variety of colors [Cr(OH)6]3- [Cr(H2O)6]3+ [Cr(NH3]3+
among transition metal

complexes has long
fascinated the observer.
eg
[Co(H2O)6]2+ [CoCl4]2- [Cr(H2O)6]3+ [Cr(H2O)6]2+
O
t2g
• Since this spacing depends (t2g and eg) on factors such as the geometry of
the complex, the nature of the ligands present, and the oxidation state of the
central metal atom,
• Dr. D. Suresh
Electronic spectra of complexes can provide valuable information related to
sureshvnr@gmail.com
bonding and structure.
88703 58876
70
Dr. D. Suresh
sureshvnr@gmail.com
88703 58876
Visible Light and Complementary Colors:
• The visible part of the electromagnetic spectrum contains light of wavelength
380-750 nm.
• The color wheel below gives information on the wavelength of different color
and also the complementary color.
• For example, if red light is absorbed, the complex appears green
Dr. D. Suresh
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88703 58876
The spectrum of the d3 complex [Cr(NH3)6]3+,
• The transitions are between orbitals that are predominantly metal d orbital in
character, with a separation characterized by the strength of the ligand-field
splitting parameter ΔO, these two transitions are called d–d transitions or
ligand-field transitions .
d3 complex [Cr(NH3)6]3+
Transition
Dr. D. Suresh
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88703 58876
73
Term Symbols for Complexes
• In the absorption spectra, the transitions are labelled as 4T2g ← 4A2g (at
21,550 cm−1) and 4T1g ← 4A2g (at 28,500 cm−1).
• The labels are molecular term symbols and serve a purpose similar to that of
atomic term symbols.
Term symbol for Complexes:
• The terms of an complex are labelled by the symmetry species of the overall
orbital state; a superscript prefix shows the spin multiplicity of the term.
Spin multiplicity 2S+1 A,E,T symmetry label of the

overall electronic orbital
A = singly degenerate
E = double degenerate
T = triply degenerate
Dr. D. Suresh
sureshvnr@gmail.com J is not mentioned
88703 58876
74
Correlating the terms for octahedral complex:
• In a free atom, where all five d orbitals in a shell are degenerate (same
energy), considering only the electron–electron repulsions is sufficient to
arrive at the relative ordering of the terms of a given dn configuration.
• In a octahedral complex, the d orbitals are not at all degenerate (due to
crystal field splitting) and it is necessary to take into account the difference in
energy between the t2g and eg orbitals as well as the electron–electron
repulsions.
Orbitals in ligand filed:
• s-orbital spherically symmetrical not affected by ligand filed

• p-orbital are affected equally by ligand filed
Dr.• D. Suresh
d-orbital are split into two by ligand filed
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• f-orbital are split into three by ligand filed
88703 58876
Atomic Number Terms in

term of states Octahedral field
S 1 A1g
P 3 T1g
D 5 Eg, T2g
Mulliken
F 7 T1g, T2g, A2g
Symbols
G 9 A1g, Eg, T2g, T1g
H 11 Eg, T1g, T1g,T2g
I 13 A1g, A2g, Eg, T1g, T1g, T2g
• The spin multiplicity of each component will be the same as that of its parent
term because the spin state of an electron is unaffected by the symmetry of
Dr. D. Suresh
an external field.
sureshvnr@gmail.com
88703 58876
76
For example, Atomic Number Terms in
term of states Octahedral field
• The term symbol for d2 configuration
S 1 A1g
is 3P, the same in octahedral field (in
P 3 T1g
presence of ligand) is given by,
D 5 Eg, T2g
• By table, P term corresponds to T1g F 7 T1g, T2g, A2g
term of octahedral complex G 9 A1g , Eg, T2g, T1g
• Multiplicity won’t change, so 3P atomic term correlates with the 3T1g term in
octahedral field
2S+1 2S+1 A or E or T
LJ
configuration atomic term Octahedral field term
3P 3T 2D
d9 2E , 2T
Dr. D. Suresh 1g
2D
5/2 g 2g
d1 2E , 2T
sureshvnr@gmail.com 3/2 g 2g
88703 58876 d3 4F 4T , 4T , 4A
77
3/2 1g 2g 2g
Term symbol for Complexes: Correlating the terms for tetrahedral complex:
• It follows exactly the same as that of tetrahedral complex, except that the
tetrahedral geometry do not have the center of symmetry.
• Hence the correlation terms do not contain the suffix “g”
• s-orbital spherically symmetrical not Atomic Number Terms in

term of states Tetrahedral field
affected by ligand filed S 1 A1
• p-orbital are affected equally P 3 T1
• d-orbital split into two D 5 E, T2
• f-orbital split into three F 7 T1 , T2 , A2
For example, G 9 A , E , T2 , T1
configuration atomic term tetrahedral field term

d9 2D 2E , 2T2
Dr. D. Suresh 2D
5/2
d1 2E , 2T2
sureshvnr@gmail.com 3/2
d3 4F 4T , 4T2 , 4A2
88703 58876 3/2 1
Dr. D. Suresh
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88703 58876
For example, d4 low spin complex,

S=
-1 -2 2
2
S= =1
2
+2 +1 0 The spin multiplicity is given by, 2S + 1
 2(1) + 1 = 3
Step 2: To calculate L Step 3: To calculate J

L = mli J = L – S when the subshell is less than half filled
L = (+2  2) + (+1  1) + (0  1) J = S when the subshell is half-filled
L=4+1+0=5=H
J=L–S=5–1=4
The term symbol is 3H4
Dr. D. Sureshto
H corresponds
Hence molecular term symbol is
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Eg+T1g + T1g + T2g
3E + 3T + 3T + 3T80
88703 58876
molecular term g 1g 1g 2g
d6; [Fe(H2O)4]2+ d6 low spin complex; [Fe(CN)6]4-
t2 -1 -2
0 -1 -2 S=0
t S=2 +2 +1 0
spin multiplicity = 2(0) + 1 = 1
e
+2 +1 L=4+2+0=6=I
spin multiplicity = 2(2) + 1 = 5 J=L+S=6+0=6
L=4+1+0–1–2=2=D The term symbol is 1I6
J=L+S=2+2=4
The term symbol is 5D4 I corresponds to A1g+A1g+Eg+T1g+T2g+T2g
D corresponds to molecular term
E2 +T2 molecular term
Dr. D. Suresh
Hence molecular term symbol is Hence molecular term symbol is
sureshvnr@gmail.com 1A +1A +1E +1T +1T +181T
5E + 5T
88703 58876
2 2
1g 1g g 1g 2g 2g
To find the ground state in Molecular Term symbol:
• In d1 case, the one electron can be written in three different ways,
eg eg eg
O O O
t2g t2g t2g

• Hence it is a triplet state with S = 1/2 and hence the ground state term is 2T2g
• In d2 case, the two electrons can be written in three different ways,
eg eg eg
O O O
Dr. D. Suresh
sureshvnr@gmail.com t2g t2g t2g
88703
• Hence it is58876
a triplet state with S = 1 and hence the ground state term is 3T2g
Term symbol for Complexes: To find the ground state in Molecular Term symbol:
• In d4 low spin case, the four electron can be written in three different ways,
eg eg eg
O O O
t2g t2g t2g

• Hence it is a triplet state with S = 1 and hence the ground state term is 3T2g
• In d4 high spin case, the four electron can be written in two different ways,
eg eg
O O
Dr. D. Suresh
sureshvnr@gmail.com t2g t2g
88703
• Hence it is58876
a double state with S = 2 and hence the ground state term is 5E2g
To find the ground state in Molecular Term symbol:
Ground terms for ML6 (Oh) and ML4 (Td) configurations:
Dr. D. Suresh
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88703 58876
d6 high spin complex; [Fe(H2O)6]2+ eg eg
-1 -2 O O
S=2
+2 +1 0 t2g t2g
spin multiplicity = 2(2) + 1 = 5 eg
L = 4 + 1 + 0 -1 – 2 = 2 = D
J=L+S=2+2=4 O
The term symbol is 5D4 t2g

D corresponds to • In d6 high spin case, the electrons can
T2g + Eg molecular term
be written in three ways,
Dr. D.
Hence Suresh
molecular term symbol is • Hence it is a triplet state with S = 2 and
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5T + 5E
88703 58876
2g g hence the ground state term is 5T2g
Hole formalism:
d1, ground state d1, excited state
• A d9 system can be
eg eg
considered as the
h
inverted d1 system as
O O
far as energy levels
can be considered t2g t2g
because d9 system has
The transition can be viewed as electron transfer from t2g to eg
an electron vacancy,
which is called a ‘ hole’.
eg eg
• So d1 and d9 are similar
h
but the energy levels are O O
inversed.
Dr. D. Suresh t2g t2g
• This is called hole
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88703 58876
formalism. The transition can be viewed as hole transfer from eg86to t2g
Hole formalism:
• While calculating the term symbol, when a sub-shell is more than half filled,
it is simple and more convenient to consider the holes (that is the vacancies
in the various orbitals).
• In general the configurations of less than half-filled and more than half filled
are related as,
pn = p6  n and dn = d10  n
• Dr. D. Suresh
Underlined one are the ground
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state electronic term symbol
88703 58876
87
பால்: பபாருட்பால் அதிகாரம்: பவருவந்தபசய்யானை குறள்: 562
கடியதாச்சி சமல்ல எறிக சநடிதாக்கம்
நீங்காவம யைண்டு பைர்
• குற்றங்கள் நிகைாமல் இருக்கக் கண்டிக்கும்யபாது கடுவம காட்டித்,
தண்டிக்கும் யபாது சமன்வம காட்டுகிறைர்களின் சசல்ைாக்குதான்
சதாய்வின்றி சநடுநாள் நீடிக்கும்.
Translation:
• For length of days with still increasing joys on Heav'n who call,
• Should raise the rod with brow severe, but let it gently fall.
Explanation:
• Dr.theD.king,
Let Suresh
who desires that his prosperity may long remain, commence his
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preliminary enquires with strictness, and then punish with mildness. 88
88703 58876
3P 3T
1g
Dr. D. Suresh
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88703 58876
Hole formalism: pn = p6  n and dn = d10  n
Selection Rule for UV-Visible spectroscopy
Spin selection rule:
• Transitions may occur from singlet to singlet, or from triplet to triplet states,
and so on, but a change in spin multiplicity is forbidden.
S = 0
Spin-allowed transitions
Spin-forbidden transitions
triplet  triplet triplet  singlet
or or
singlet  singlet singlet  triplet
3T  3 T2g
1g
3T  3A allowed
1g 2g
3T  3 T (P)
1g 2g
4 ADr.
D. Suresh
2 E forbidden allowed forbidden
2g g
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90
Only one electron is involved in any transition
Laporte selection rule:
• There must be a change in the parity (symmetry) of the complex
l =  1
Laporte-allowed transitions Laporte-forbidden transitions
gu gg
or or
ug uu
g stands for gerade – compound with a center of symmetry

u stands for ungerade – compound without a center of symmetry
allowed transitions are s  p, p  d, d  f l = + 1

forbidden transitions are s  s, p  p, d  d, f  f , s  d, p  f etc
Dr. D. Suresh l = 0 l = 2
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91
Only one electron is involved in any transition
Laporte selection rule:
• All the d orbitals have gerade (g) symmetry in centro-symmetric molecules,
this means that all d-d transitions in octahedral complexes are formally
forbidden.
• However, there are various mechanisms by which selection rules can be
relaxed so that transitions can occur, even if only at low intensities.
• Vibronic coupling  involves the interaction between electronic and

nuclear vibrational motion.
• Spin-orbit coupling  involves interaction of a particle's spin with its
motion
• Geometry relaxation during transition
• For example, unsymmetrical vibrations of an octahedral complex can
Dr. D. Suresh
temporarily destroy its center of symmetry and allow transitions.
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• Such vibronic transitions will be observable, though weak.
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92
For tetrahedral complexes:
• In tetrahedral complexes, there is no center of symmetry and thus orbitals
have no “g” or ‘’u” designation.
• However, the atomic orbitals from which the e and t2 orbitals are derived do
have parity properties that have a bearing on the molecular orbitals.
• The non-bonding “e” orbitals are purely metal d atomic orbitals and hence
retain their g character even in the complex.
• The “t2” molecular orbitals on the other hand, are formed from atomic d
(gerade) and p (ungerade) orbitals.
• Through this d-p mixing, which imparts some “u” character to the t2 level in
the complex, the Laporte selection rule is relaxed.
• Dr.molar
The D. Suresh
extinction coefficients () for tetrahedral complexes are about 100
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times greater than those for octahedral complexes. (Laporte partly allowed)
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93
• The tetrahedral complexes are Laporte rule is partly-allowed and hence they
are strongly colored than octahedral complex.
• The unsymmetrically substituted octahedral complexes are also Laporte
allowed (partly) and hence they are intensely colored (due to d-orbital and p-
orbital mixing).
• [MX4]y – tetrahedral complexes are coloured and will have  are in the
range of 20 – 100. For example, [Cu(NH3)4]2+
• [ML6]y – octahedral complexes with Oh symmetry are not coloured and will
have  are in the range of 0.02. For example, [Cu(NH3)6]2+

y octahedral complexes without O symmetry are coloured and will
• Dr.5X]
[ML D. –Suresh h
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have  are in the range of 20 – 100. For example, [Cu(NH3)5(H2O)]2+
88703 58876
94
Indicator silica gel:
• Silica gel may be doped with a moisture indicator that gradually changes its
color when it transitions from the anhydrous (dry) state, to the hydrated (wet)
state.
• Common indicator is cobalt(II) chloride.
• Cobalt (II) chloride is deep blue when dry and pink when wet ([Co[(H2O)6]2+).
light pink
deep blue octahedral [Co(H2O)6]2
tetrahedral CoCl42-
Dr. D. Suresh
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88703 58876[CoCl4]2- + 6 H2O  [Co[(H2O)6]2+ + 4Cl-
Expected intensities of electronic transitions:
Higher the “” value, the intensity is higher and it will be an

allowed transition.
Dr. D. Suresh
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96
Expected intensities of electronic transitions:
Completely
forbidden
transition
Centrosymmetric
Octahedral
complexes
Non-Centrosymmetric
tetrahedral molecules
Completely
allowed
transition
Dr. D. Suresh
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88703Increasing
58876 intensity
Interpretation of Electronic Spectra of Complexes
Dr. D. Suresh
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88703 58876
For d1 high spin octahedral metal complex:
d1, ground state d1, excited state Complexes , (cm-1)
eg [Ti(Cl)6]3+ 18,900
eg
[Ti(F)6]3+ 20,300
h
[Ti(H2O)6]3+ 20,300
O O
[Ti(CN)6]3- 22,300
t2g t2g
• Depends on the ligands, the O changed and hence the affects the energy of
transition.
• This is how the spectrochemical series generated. 2E
g
+6 Dq
Dr. D. Suresh 2T -4 Dq
sureshvnr@gmail.com 2g
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99
d1, ground state d1, excited state 2E

g
eg eg +6 Dq
h
O O
2T -4 Dq
2g
t2g t2g
• Term symbol for d1 is 2D which in presence One peak
of ligands changed to 2T2g and 2Eg 2T

2g  2Eg
Dr. D. Suresh 2T
2g  2Eg
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100
= hole or vacant place
eg eg
• Here, the transition can be
h
viewed as transferring of hole
O O
from eg to t2g.
t2g t2g • Therefore the energy level
diagram will be exactly the
• Term symbol for d9 is 2D which in same as that of d1 but with
presence of ligands changed to inverse order.
2T
2g and 2Eg One peak
2T
2g 2E  2T
g 2g
+4 Dq
Dr. D. Suresh -6 Dq
sureshvnr@gmail.com 2E
g
2E  2T2g
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101
g
For d6 and d4 high spin octahedral metal complex:
• The d6 and d4 octahedral configurations are exactly similar to d1 and d9
octahedral configurations respectively (d1 = d6 and d4 = d9).
d6, ground state d6, excited state Similar to d1 system
eg eg
h
O O
promoting one electron
from t2g to eg
t2g t2g
Similar to d9 system
eg
O
Dr. D. Suresh
h O
sureshvnr@gmail.com hole transfer from
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102
t2g t2g from eg to t2g
Orgel diagram for d1, d4, d6 and d9 octahedral configuration in high
spin metal complex
d4 = d9 d1 = d6
Dr. Hence,
D. Suresh
only one peak will be there in the absorption spectra for
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these configurations
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103
For d1, d4, d6 and d9 tetrahedral complex:
• The d1 tetrahedral complex is equal to that of d4 octahedral configurations.
• That is d1 (Td) = d4 (Oh) One peak
2E  2T2
t2 t2
h
t t
promoting one electron

e e
from e to t2
Dr.Similar
D. Suresh
to promoting one hole
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d4 octahedral system
from eg to t2g
88703 58876
For d1, d4, d6 and d9 tetrahedral complex:
• Similarly, d1, d6 (Td) = d4, d9 (Oh) & d4, d9 (Td) = d1, d6 (Oh)
Orgel diagram for d1, d4, d6 and d9 tetrahedral high spin metal complex
d1 = d6 d4 = d9
Dr. D. Suresh
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88703 58876
Orgel diagram for d1, d4, d6 and d9 octahedral and tetrahedral of
high spin metal complex
d1, d6 – Tetrahedral d4, d9 – Tetrahedral
d4, d9 – Octahedral d1, d6 – Octahedral
Dr. D. Suresh
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Increasing  value (depending on ligand) Increasing  value (depending on ligand)
88703 58876
Orgel diagram for d1, d4, d6 and d9 octahedral and tetrahedral complexes:
• In all these cases, only one electronic transition from a ground to excited
state is possible. i.e only one peak
• for octahedral d1 and d6, the transition is Eg  T2g
• for octahedral d4 and d9, the transition is T2g  Eg
• for tetrahedral d1 and d6, the transition is T2  E
• for tetrahedral d4 and d9, the transition is E  T2
• Each transition is spin-allowed (no

change in total spin, S) and the
electronic absorption spectrum of
each ion exhibits one band.
Dr. D. Suresh • The transitions were included with
sureshvnr@gmail.com spin multiplicities, 2S + 1,
88703 58876
gu triplet  triplet
or or
ug singlet  singlet
• for octahedral d1 and d6, the transition is Eg  T2g
• for octahedral d4 and d9, the transition is T2g  Eg
• for tetrahedral d1 and d6, the transition is T2  E
• for tetrahedral d4 and d9, the transition is E  T2
Dr. D. Suresh
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88703 58876
For d2 octahedral high spin complexes:
• For a d2 system, there are 45 (1G (9), 3F (21), 1D (5), 3P (9), and 1S (1))
microstates are possible.
• For interpreting electronic spectra, it is necessary to concern with the terms
of maximum spin multiplicity (3F and 3P ).
• Since, higher the spin multiplicity corresponds to lower the energy and falls
in the UV-Visible region.
• The 3F term is expected to be lower in energy than the 3P term. (higher the
L value, lower the energy).
• In presence of ligands in octahedral field,
the term 3P do not spilt and it has the
octahedral term is 3T1g (P)
• Dr. D.3FSuresh
While, term split into 3T1g (F), 3T2g (F)
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and 3Ag (F)
88703 58876
Term Term in Oh field Configuration Same electronic
3P 3T configuration but
1g (P) t2g1 eg1 electrons are different
3T orbital.
1g (F) t2g2 eg0
3F So varies in energy
3T t2g1 eg1
2g (F)
3A (F) t2g0 eg2
g
t2g2 eg0
dz2 dx2-y2 dz2 dx2-y2 dz2 dx2-y2

eg eg eg
t2g2 eg0= 3T1g (F)
triply degenerate
O or O or O because there are
three ways of placing
Dr.d D. Suresh two electrons
dxy dyz t2g dxy dxz dyz t2g dxy dxz dyz t2g
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xz
ground state
88703 58876
t2g1 eg1
dz2 dx2-y2 dz2 dz2
dx2-y2 dx2-y2 t2g2 eg1= 3T2g (F)
eg eg eg
triply degenerate
two electrons
dxy dxz dyz t2g dxy dxz dyz t2g dxy dxz dyz t2g
excited state
dz2 dx2-y2 dz2 dx2-y2 dz2 dx2-y2
eg eg eg t 2 e 1= 3T (P)
2g g 1g
triply degenerate
Dr. D. Suresh two electrons
t t2g t2g
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dxy dxz dyz 2g dxy dxz dyz dxy dxz dyz
88703 58876 excited state
dz2
t2g0 eg2 dx2-y2
eg
Only one way the
two electrons can
O be arranged. t2g0 eg2 = 3A2g (F)
singly degenerate
t2g
dxy dxz dyz
excited state
• The energies are given as follows,
3T (F) < 3T2g (F) < 3T1g (P) < 3A2g (F)
1g
• The 3T2g (F) and 3T1g (P) terms equate with a t2g1eg1 configuration; the lower
energy 3T2g (F) term arises from placing two electrons in orbitals lying in
mutually perpendicular planes, e.g. (dxy)1(dz2)1, while the higher energy 3T1g
Dr. D. Suresh
(P) term arises from placing two electrons in orbitals lying in the same plane
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88703 58876
e.g. (d ) 1(d 2 2)1.
xy x -y
3A
2g (F)
Energy
3T (P)
1g
3T (F)
1g
h 3T (F)
Dr. D. Suresh
2g
• Hence, three transitions are possible

sureshvnr@gmail.com
88703 58876 and three peaks will appear.
Orgel diagram for d2 octahedral high spin complexes:
• Energies of the 3T1g (F) < 3T2g (F) < 3T1g (P) < 3A2g (F) terms are given as,
• Hence, three transitions are possible and three peaks will appear.
3A (F)  3T (F) 3T (F)  3T (F) (lower energy)

2g 1g 2g 1g
(P)
3T (P)  3T (F) (higher energy)
1g 1g
3A (F)  3T (F) (highest energy)
2g 1g
3T (P)  3T (F)
1g 1g
3A
2g (F)  3T1g (F)
3T
1g (P)  3T1g (F)
3T
2g (F)  3T1g (F)
3 3
Dr.TD. Suresh
2g (F)  T1g (F)
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Increasing  value
(F)
88703
(depending58876
on ligand) E  frequency number
Orgel diagram for d2 octahedral high spin complexes:
• Starting with that d2, d7 – Octahedral
d3, d8 – Octahedral
diagram and using
the same
(P)
arguments of hole (P)
formalism, the
complete set of (F)
Orgel diagram for
d2, d3, d7 and d8
octahedral (high
spin) and
(F)
Dr. D. Suresh
tetrahedral
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complex is, Increasing  value Increasing  value
88703 58876 (depending on ligand) (depending on ligand)
Orgel diagram for d2, d3, d7 and d8 octahedral (high spin)
and tetrahedral complexes
d3, d8 – Octahedral d2, d7 – Octahedral
(P)
(P)
(F)
(F)
Dr. D. Suresh
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Increasing  value Increasing  value
88703
(depending 58876
on ligand) (depending on ligand)
Orgel diagram for d2, d3, d7 and d8 octahedral (high spin) and tetrahedral
complexes:
• From Orgel diagram, it is

clear that three absorptions (P) (P)
peaks are observed in the
electronic spectra of d2, d3, (F)
d7 and d8 octahedral and
tetrahedral complexes.
(F)
• The transitions are from the
ground to excited states, and
Dr.allD.
are Suresh (S = 0).
spin-allowed
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88703 58876
For d5 configuration:
eg
eg
h
O O
Most of d5 system are
t2g colourless or show very
t2g
weak absorption
Forbidden transition
(Spin selection rule)
For d10 configuration:

eg The orbitals are completely
symmetry and non-degenerate
Dr. D. Suresh O Most of d10 system are

sureshvnr@gmail.com colourless or show very
weak absorption 118
88703 58876 t2g
• Some important points are that the electronic absorption spectra of high spin
complexes are as follows,
• By Orgel diagram,
• d1, d4, d6 and d9 complexes consist of one broad absorption;
• d2, d3, d7 and d8 complexes consist of three broad absorptions;
• d5 complexes consist of a series of very weak and relatively sharp
absorptions.
Limitations of Orgel diagram:

• They treat only for high spin complexes.
• Only useful for spin allowed transitions when the number of peaks are
greater than or equal to empirical parameters.
Dr. D. Suresh
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119
Orgel diagram
d1, d4, d6 and d9
complexes consist of
one broad absorption
(P) (P)
d2, d3, d7 and d8
complexes consist of (F)
three broad absorptions
Dr. D. Suresh (F)

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120
(P) (P)
(F)
(F)
3T
2g (F)  3A2g (F)
3T
1g (F)  3A2g (F)
3T
1g (P)  3A2g (F)
Dr. D. Suresh
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121
500 900
Broadening of absorption peak:
• The single absorption band is quite broad and can be attributed mainly to
the fact that the complex is not a rigid, static structure.
• The metal-ligand bonds are constantly vibrating, with the result that an
absorption peak is integrated over a collection of molecules with slightly
different molecular structures and o values.
• Such ligand motions will be exaggerated through molecular collisions in
solution, in the solid stale, however, it is sometimes possible to resolve
spectral bands into their vibrational components.
• Dr. D. Suresh
Spin-orbit coupling and Jahn- Teller effect can also result in broadening of
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88703 58876
122
absorption spectra.
CSIR June 2013
CSIR December 2015
CSIR December 2014 CSIR July 2015
Dr. D. Suresh
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123
GATE 2008
GATE 2010
GATE 2015
CSIR December 2017
GATE 2011
Dr. D. Suresh
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124
GATE 2016
CSIR June 2014
GATE 2013
CSIR July 2012
Dr. D. Suresh
sureshvnr@gmail.com
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125
HCU, 2014
HCU-MSC, 2014
HCU, 2017
Dr. D. Suresh
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88703 58876
HCU, 2017
GATE 2018
Dr. D. Suresh
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88703 58876
பால்: பபாருட்பால் அதிகாரம்: காலைறிதல் குறள்: 482
பருைத்யதாடு ஒட்ட ஒழுகல் திருவிவனத்
தீராவம ஆர்க்குங் கயிறு
• காலம் உணர்ந்து அதற்யகற்பச் சசயல்படுதல், அந்த நற்சசயலின்
சைற்றிவய நழுைவிடாமல் கட்டிப்பிணிக்கும் கயிறாக அவமயும்.
Translation:
• The bond binds fortune fast is ordered effort made,
• Strictly observant still of favouring season's aid.
Explanation:
• Dr. D.
Acting at Suresh
the right season, is a cord that will immoveably bind success (to a
sureshvnr@gmail.com
king). 128
88703 58876
Orgel diagram
d1, d4, d6 and d9
(P) (P)
d2, d3, d7 and d8
complexes consist of (F)
Dr. D. Suresh (F)

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88703 58876
Use of Racah parameters to measure o:
• For a d1 and d9 configuration, the energy of the

absorption band in an electronic spectrum gives a
direct measure o.
• For electron configurations other than d1 and d9, the situation is more
complicated because there will be some electrostatic repulsion between
those electrons.
• The amount of repulsion varies from atom to atom, depending upon the
number and spin of the electrons and the orbitals they occupy.
• The total repulsion parameter are linear combinations of certain coulomb
and exchange integrals.
• Dr.total
The D. Suresh
repulsion can be expressed in terms of three parameters A, B and
sureshvnr@gmail.com
C which are known as the Racah parameters.
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130
• The term “A” corresponds to the partial shift of all terms of a given electronic
configuration. (not taken into account for spectroscopy)
• The terms “B” and “C” measure of spatial arrangement of the orbitals of the
ligand and the metal ion (electronic repulsion of d-electrons).
• The decrease in the value of the inter-electronic repulsion parameter, B,
leads to formation of partially covalent bonding. “nephelauxetic” = “cloud-expanding”
• Lower the value of “B” more the covalency of M—L bond.
• The ratio between the crystal B parameter and the free ion B parameter is
known as nephelauxetic ratio and it is denoted by .

Dr. D. Suresh
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• The value of  is a measure of covalency. (higher , more the covalency)
88703 58876
131
B’complex
Nephelauxetic ratio () =
B free ion
Nephelauxetic series for ligands:
fluorides tend to be very ionic, less  value more B value
Nephelauxetic series for metal ions (irrespective of ligands):
Dr. D. Suresh
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132
Use of Racah parameters:
Bfree ion− B′complex
• The reduction in the inter-electronic repulsion ( )
Bfree ion
can be calculated by using the equation,
Reduction in inter-electronic repulsion ( )  hligands  kmetal
Bfree ion
• For example the reduction in inter-

electronic repulsion in going from
the gaseous Fe3+ ion to [FeF6]3- is
about 19%.

( )  hligands  kmetal
Bfree ion
 0.8  0.24
Dr. D. Suresh
sureshvnr@gmail.com  0.192 = 19.2 %
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133
“A” is ignored because it is roughly the same for all
the metal center
Related electron “B” represents is an approximation of the bond
repulsion and varies strength between the ligand and metal
with metal and number
of electrons “C” generally approximated as being 4B
• Utilizing these, in order to find the o, we have to use the Tanabe-Sugano
(TS) diagrams.
• The energy of the ground state is taken to be zero for all field strengths, and
the energies of all other terms and their components are plotted with respect
to the ground term.
• Two terms of the same symmetry upon increase of ligand field strength bend
Dr. D. Suresh
apart from each other
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• TS is a plot of E/B (y-axis) Vs o/B (x-axis)
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134
For d2 complex including the electronic repulsion:
Energy
free
metal ion
L-S
Dr. D. Suresh
coupling weak filed
sureshvnr@gmail.com(high spin) strong filed (low spin)
88703 58876 octahedral octahedral
Tanabe-Sugano Diagrams:
d2 with C = 4.428B d3 with C = 4.502B
Dr. D. Suresh
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136
d4 with C = 4.611B d5 with C = 4.477B
Dr. D. Suresh
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137
d6 with C = 4.808B
d7 with C = 4.633B
Dr. D. Suresh
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138
d8 with C = 4.709B
Allowed transitions?
Dr. D. Suresh
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139
• The x-axis in a Tanabe-Sugano diagram is in terms of the crystal field
splitting parameter and Racah parameter, 10Dq/B, or Δo/B.
• The y-axis is in terms of energy of a electronic transition, E/B.
• Each line represents the energy of an electronic state while varying the
strength of octahedral ligand field.
• However only a few electronic states are spin allowed.
• The spin forbidden electron transitions are included since spin forbidden
transitions can appear in spectrum.
• Each term symbol is created from the splitting of term symbols from
Dr. D. Suresh
spherical to octahedral symmetry and with the relative energy ordering of the
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states.
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140
Using TS Diagrams:
Step:1 The dn-configuration of the metal ion is to be find.
Step:2 Select the appropriate TS diagram matching the dn-configuration.
Step:3 Take a spectrum of the complex and identify max (absorption
maximum) for spin-allowed (strong intensity) and spin forbidden (weak
intensity) transitions.
Step:4 Convert max to wavenumbers and generate energy ratios relative to
the lowest allowed transition. (i.e. E2/E1and E3/E1)
E1 is lowest energy and E2, E3….. subsequent higher energies
Step:5 Using a ruler, slide it across the printed diagram until the E/B ratios
between lines is equivalent to the ratios found in the step 4.
Step:6 Solve for B using the E/B values (y-axis, step 4) and Δo/B (x-axis, step
Dr. D. Suresh
sureshvnr@gmail.com
5) to yield the ligand field splitting energy 10Dq or Δo.
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141
https://chem.libretexts.org/Core/Inorganic_Chemistry/Crystal_Field_Theory/Tanabe-Sugano_Diagrams
Using TS Diagrams:
1 1
= =
1250 𝑛𝑚 1250 ×10−9 𝑚
1
Dr. D.=Suresh
1250 𝑛𝑚
= 8,00,000 m-1
sureshvnr@gmail.com
-1
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= 8,000 cm 142
Using TS Diagrams:
Allowed transitions are,

4T (F)  4A ( ) 4T (F)  4A2g (2)
2g 2g 1 1g
4T (P)  4A2g (3)

1g
(E3) (E3/E1)
Dr. D. Suresh (E2) (E2/E1)

sureshvnr@gmail.com (E1) (E1/E143
1)
88703 58876
Using TS Diagrams:
Allowed transitions are,
d3-TS Diagrams
4T (F)  4A ( ) 4T (F)  4A2g (2)
2g 2g 1 1g
4T (P)  4A2g (3)

64 1g
45
29
Dr. D. Suresh
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144
Using of TS Diagrams:
E/B
E/B = 29
B = E/29
= 23200/29
= 800
o/B = 10; O = 10  B
o = 10  800 = 8000
• The graphical methods (above method) however are somewhat lacking in
Dr. D. Suresh
precision compared to algebraic solutions.
sureshvnr@gmail.com
• Hence,
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the numerical algebraic equations are used to find the exact 145
values.
Numerical methods to calculate B’complex,  and Δo (10Dq):
• For the complexes with A2 term ground state ions,
Observed transitions 10Dq or o B
1, 2, 3
1 (3+2  31)/15
(all three translons are observed)
1, 2 (2  21)(2  1)/3(52  91)
(only two translons are observed) 1
1, 3 (3  21)(3  1)/3(53  91)

(only two translons are observed) 1
2, 3 (2 + 3  3(10Dq or o)/15

[9(2+3)  {85 (23)2)  4(2+3)2}1/2/34
(only two translons are observed)
J. Chem. Educ., 1990, 67, 134
• For the complexes with T1 term ground state ions, DOI: 10.1021/ed067p134
Observed transitions 10Dq or o B

1, 2, 3
2  1 (3+2  31)/15
(all three translons are observed)
1, 2  1(2  21)/3(42  91)
(only two translons are observed) 2  1
1, 3 (3  21 + 10Dq or o)/15

Dr. D. Suresh
[(532  (3  21)2)1/2  2(3  21)]/4
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2, 3
[(8532  (3  22)2)1/2  9(3  22)]/34
(3  22  3(10Dq or o)/15
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1 1
= =
1250 𝑛𝑚 1250 ×10−9 𝑚
1
Dr. D.=Suresh
1250 𝑛𝑚
= 8,00,000 m-1
sureshvnr@gmail.com
-1
88703 58876
= 8,000 cm 147
3 d3-TS Diagrams
For d octahedral configuration,
(A2 ground term)
All three transitions are observed (1 to 3)
The formula to be used are,
3 + 2 − 31
B’(complex) = cm-1
15
10Dq =Δo = 1
23200 + 13600− 3(8000)

15
B’(complex) = 853 cm-1
Dr. D. Suresh
8000
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10Dq =Δo = cm−1
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148
Numerical methods to calculate B’complex,  and 10Dq:
• Calculate the 10Dq, B’ and  values for the complex, [V(H2O)6]3+ which
shows three transitions of 1, 2 and 3 at 17,400 cm-1, 25,200 cm-1 and
34,500 cm-1, respectively. The B value for the free V3+ ion is 1056 cm-1.
Step: 1 3 + 2 − 31
15
34,500 +25,200 − 3(17,400)
15
B’(complex) = 500 cm-1
Step: 2 B’complex 500

= = = 0.4734
B free ion 1056
 = 0.4734
Step: 3 10Dq = 2 − 1
For dDr. D. Suresh
2 octahedral configuration, = 25,200 - 17,400
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(T1 ground term) 10Dq = 7,800 cm-1
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149
Numerical methods to calculate B’complex,  and 10Dq:
 + 2 − 31 If wavelength in nm is
Step: 1 B’(complex) = 3 cm-1
15 given, convert them to
wave number in cm-1
Step: 2 B’complex
=
B free ion
Step: 3 To find the ground term (A2 or T1)
If A2 is ground term then If T1 is ground term then

10Dq = 1 10Dq = 2 − 1
Dr. D. Suresh
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150
Orgel Vs Tanabe-Sugano Diagrams
Orgel Tanabe-Sugano
• Splitting of free ion term in weak • Splitting of free ion term in both weak
field alone considered and strong field alone considered
• Plot is E Vs Dq • Plot is E/B Vs Dq/B
• Ground state term is not taken as
• Ground state term is the base line
base line
• Splitting patterns of high energy • Splitting patterns of high energy
terms are not considered terms are considered
• Only for allowed transition can be • Both allowed and forbidden transition
interpreted can be interpreted
Dr. D. Suresh
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151
CSIR December 2015
3 + 2 − 31
HCU, 2016 15
Dr. D. Suresh
sureshvnr@gmail.com
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152
பால்: பபாருட்பால் அதிகாரம்: புல்லறிவாண்னை குறள்: 847
அருமவற யசாரும் அறிவிலான் சசய்யும்
சபருமிவற தாயன தனக்கு
• நல்ைழிக்கான அறிவுவரகவைப் யபாற்றி அவ்ைழி நடக்காத
அறிவிலிகள், தமக்குத் தாயம சபருந்துன்பத்வதத் யதடிக்
சகாள்ைார்கள்.
Translation:
• From out his soul who lets the mystic teachings die,
• Entails upon himself abiding misery.
Explanation:
• Dr.fool
The D. Suresh
who neglects precious counsel does, of his own accord, a great
injury to himself.
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TS diagram
B’complex
=
B free ion
Dr. D. Suresh
sureshvnr@gmail.com
88703 58876
Tetragonally distorted complexes: Jahn–Teller effect
• A tetragonal distortion can be expected when the ground electronic
configuration of a complex is orbitally degenerate; the complex will distort so
as to remove the degeneracy and achieve a lower energy.
• For both d1 and d9 it is expected to exhibit

one absorption band corresponding to
excitation of an electron from the t2g to the
eg or eg to t2g levels . hump or shoulder peak
• However these coordination compounds

exhibit two closely overlapping absorption
bands rather than a single band.
• Dr. is
This D.called
Sureshas a hump or the shoulder
sureshvnr@gmail.com
peak.
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155
• Jahn and Teller showed that non-linear molecules having a degenerate

electronic state should distort to lower the symmetry of the molecule and
reduce the degeneracy; this is the Jahn–Teller theorem
D4h D4h
Oh
eg
Jahn–Teller
or
distortion
 t2g
Dr. D. Suresh Z-out Z-in

sureshvnr@gmail.com or Or
88703 58876 Elongation compression
• Octahedral, a non-
linear molecule, and
having unsymmetrical
electron arrangement
in the eg level lead to
distort tetragonally.
• Resulting in the
collapse of regular
octahedral geometry
and the hence M-L
bond distance are vary.
• Resulting a shoulder
Dr. D. Suresh Z-in Z-out
peak in UV or
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Elongation
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157
spectroscopy. compression
Z-out
Z-in or
or Elongation
Dr. D. Suresh
Compression
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88703 58876
eg eg eg eg
t2g t2g t2g t2g
• Have unsymmetrical electron • Have symmetrical electron

arrangement in either t2g or eg level. arrangement in either t2g or eg level.
• These configurations undergo • These configurations do not
tetragonal distortion. undergo tetragonal distortion.
• Shoulder peak is observed in UV • No shoulder peak is observed in
spectroscopy. UV spectroscopy.
• Unsymmetrical electron arrangement in eg level shows stronger distortion

Dr.hence
and D. Suresh
strong Jahn-Teller distortion (Static).
sureshvnr@gmail.com
• This is due to eg level is much more involved in the  bonding than the
159t .
88703 58876 2g
Static Jahn-Teller distortion:
• Some molecules show tetragonal shape under all conditions i.e., in solid
state and in solution state; at lower and relatively higher temperatures.
• Hence the distortion is strong (permanent)
• This is referred to as static Jahn-Teller distortion.
• It is observed when the degeneracy (unsymmetrical arrangement in eg)
occurs in eg orbitals.
Unsymmetrical
arrangement
in eg
Dr. D. Suresh
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88703 58876
Dynamic Jahn-Teller distortion:
• In some molecules, the distortion is not seen either due to random
movements of bonds which does not allow the measurement within a time
frame or else the distortion is so weak as to be negligible.
• However the distortion can be seen by freezing the molecule at lower
temperatures.
• Hence the distortion is weak (temporary)
• This condition is referred to as dynamic Jahn-Teller distortion.
• It is observed when the degeneracy (unsymmetrical arrangement in eg)
occurs in eg orbitals.
Unsymmetrical
Dr. D. Suresh arrangement
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161
High Spin complexes:
 Yes  No
 Yes  Yes  No
 Yes  Yes  No  Yes  No
 No – Symmetrical arrangement – No Jahn-Teller distortion observed

Dr. D. Suresh
 Yes – Unsymmetrical arrangement – Yes Jahn Teller distortion observed
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162
Configuration in the box show strong (static) Jahn Teller distortion
Low Spin complexes:
 Yes  Yes  No  Yes  Yes
 No  Yes  No  Yes  No
 No – Symmetrical arrangement – No Jahn-Teller distortion observed

Dr. D. Suresh
 Yes – Unsymmetrical arrangement – Yes Jahn Teller distortion observed
sureshvnr@gmail.com
88703 58876
163
Configuration in the box show strong (static) Jahn Teller distortion
Dr. D. Suresh
sureshvnr@gmail.com
88703 58876
164
Steps to follow,
Step: 1 Find the oxidation state of the metal and its d-electron
Step: 2 Identify the type of ligands strong/weak
Step: 3 Accordingly fill the electrons in the t2g and eg orbitals
For example, [Cr(H2O)6]2+

Step: 1 Find the oxidation state of the metal and its d-electron
Cr is in +2 oxidation state and number of d-electron is 4
Step: 2 Identify the type of ligands strong/weak and the complex

H2O weak ligand and for high spin complex
Step: 3 Accordingly fill the electrons in the t2g and eg orbitals
Dr. D. Suresh Unsymmetry in eg hence,

sureshvnr@gmail.com strong or static
Jahn-Teller distortion
88703 58876
• The Jahn–Teller effect identifies an unstable geometry but it does not predict
the preferred distortion (Z-in or Z-out distortion).
• For instance, with an octahedral complex, instead of axial elongation and
equatorial compression the degeneracy can also be removed by axial
compression and equatorial elongation.
• That is two longer and four shorter bond
distance (Z-out or Z-elongation) or is two
shorter and four longer bond distance (Z-
in or Z-compression).
• This can be detected only through
crystallographically at room temperature.
•
Dr. D. Suresh
Which distortion occurs in practice is a
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matter of energetics, not symmetry.
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166
• Elongation along z-axis (Z-out) is the most common distortion observed

• The axial elongation weakens only two bonds (Z-out or Z-elongation) but
Dr. D. Suresh
equatorial elongation weakens four (Z-in or Z-compression).
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• Hence
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, Z-out is more common than Z-in. 167
Dr. D. Suresh
sureshvnr@gmail.com
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Dr. D. Suresh
sureshvnr@gmail.com
88703 58876
CSIR December 2015 CSIR December 2017
CSIR June 2015
GATE 2008
Dr. D. Suresh
sureshvnr@gmail.com
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170
GATE 2010
GATE 2011
GATE 2014
GATE 2015
Dr. D. Suresh
sureshvnr@gmail.com
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171
HCU, 2016
HCU, 2015
HCU, 2010
Dr. D. Suresh
sureshvnr@gmail.com
88703 58876
HCU, 2017
Dr. D. Suresh
sureshvnr@gmail.com
88703 58876
பால்: அறத்துப்பால் அதிகாரம்: நடுவு நினலனை குறள்: 116
சகடுைல்யான் என்பது அறிகதன் சநஞ்சம்
நடுசைாரீஇ அல்ல சசயின்
• தன் சநஞ்சம் நீதிவய விட்டுவிட்டு அநீதி சசய்ய எண்ணினால்,
அதுயை தான் சகடப் யபாைதற்கு உரிய அறிகுறி.
Translation:
• If, right deserting, heart to evil turn,
• Let man impending ruin's sign discern!.
Explanation:
• Dr.him
Let D. whose
Sureshmind departing from equity commits sin well consider thus
within himself, "I shall perish.".
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Unsymmetrical
arrangement
in eg
Strong or static or permanent
Unsymmetrical
arrangement
in t2g
weak or dynamic or temporary
Dr. D. Suresh
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88703 58876
Color of Transition Metal Complexes
Cu2+; d9
dd transition
egt2g (hole transfer)
Ni2+; d9
dd transition
t2g eg (electron transfer)
Mn7+; d0
Charge transfer
Dr. D. Suresh Cr6+; d0

sureshvnr@gmail.com Charge transfer
88703 58876
Charge-Transfer Spectra
• Charge-transfer (CT) bands arise from the movement of electrons between
orbitals that are predominantly ligand in character and orbitals that are
predominantly metal in character; such transitions are identified by their high
intensity and the sensitivity of their energies to solvent polarity.
• Coordination compounds often exhibit strong eg
charge-transfer absorptions in the ultraviolet and/or

O
visible portions of the spectrum.
• Such absorption bands involve the transfer of t2g
electrons from molecular orbitals that are primarily
ligand in character to orbitals that are primarily 
metal in character, or vice versa
• Dr.charge
The D. Suresh
transfer bands, the absorptions are much more intense than d–d
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transitions and its molar absorptivity's () of 50,000 Lmol-1cm-1 or greater.
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177
LMCT and MLCT:
high intensity
eg
t2g weak intensity
Dr. D. Suresh
sureshvnr@gmail.com
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178
Ligand to metal charge transfer (LMCT):
• Electrons can be excited, not only from the t2g level to the eg, but also from
the “” orbitals originating from the ligands to the t2g and/or eg.
• The latter excitation results in a charge transfer transition, designated as
ligand to metal charge transfer (LMCT) (also called charge transfer to metal,
CTTM) .
• This type of transition results in formal reduction of the metal.
• LMCT transitions are observed in visible region of the spectrum when the,
• metal is in a high oxidation state
• ligands contain non-bonding electrons;
• Dr. D. Suresh
Variation in the position of LMCT bands can be correlated with the order of
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the electrochemical series.
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179
Ligand to metal charge transfer (LMCT): [IrBr6]2- (d5)
eg
• The octahedral complexes [IrBr6]2- (d5)
270 nm
and [IrBr6]3- (d6) both show charge- O
E
transfer bands.
t2g
• For [IrBr6]2-, two bands appear, near 600 E 600 nm
nm and near 270 nm; the former is 
attributed to transitions to the t2g levels
and the latter to the eg. [IrBr6]3-(d6)
eg
• In [IrBr6]3- the t2g levels are filled, and the only 250 nm
O
possible LMCT absorption is therefore to the eg. E
Strong absorption is seen near 250 nm, t2g
Dr. D. Suresh
corresponding to charge transfer to eg .
sureshvnr@gmail.com
88703 58876 
• The tetra oxido-anions of metals with high oxidation numbers (such as
[MnO4]−) are the most important examples of LMCT bands.
• In these, oxygen lone pair electron is

promoted into a low-lying empty metal e
orbital.
• Higher metal oxidation numbers
correspond to a low d-orbital population
(many are formally d0), so the acceptor
level is available and low in energy.
• The trend in LMCT energies is:
Dr. D. Suresh
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181
• The isoelectronic tetrahedral ions VO43, CrO42, and MnO4 all have
intense charge-transfer transitions. (moving left to right)
• The wavelengths of these transitions increase in this series, with MnO4
having its charge-transfer absorption at the longest wavelength (lower in
energy).
• This due to the fact that O increased with increasing oxidation state of the
transition metal.
• Thus the wavelengths of these transitions (ligand -orbital to e orbital of
Dr. D. Suresh
metal) decreased (high energy) as the oxidation state of the metal
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88703 58876
decreased.
d0 Mn+7 d0 Cr+6 d0 V+5

t2
t2
t2
O O O
e
e High energy, colourless
e moderate energy, yellow E
Low energy, purple
E E
  
Dr. D. Suresh  (528 nm) > CrO 2 (373 nm) > VO 3

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Wavelength of absorption, MnO4 4 4
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183
• The isoelectronic ions MnO4, TcO4 and ReO4 all have intense charge-
transfer transitions (moving down the group).
• But only the MnO4 will appear in visible light region and others wont show
any color.
• This due to the fact that O increased from first row to third row and hence
Dr. D. Suresh
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the wavelengths of these transitions decreased down the group.
88703 58876
d0 Mn+7 d0 Tc+7 d0 Re+7

t2
t2
t2
O O O
e
e
e
E
E
E
  
High energy Lower energy Lowest energy
Falls in visible light Falls outside the visible Falls outside the visible
light region light region.
Dr. purple
region, D. Suresh
colour
So colourless So colourless
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absorption, MnO4 (528 nm) < TcO4 (286 nm) < ReO4(227 nm)
88703of58876
Wavelength
Oxidation of power of reagents: higher the
oxidation state
of metal easy
3d metals to reduce
are easy (+ 5) (+ 6) (+ 7)
to reduce (easily gain
3d VO43 < CrO42 < MnO4 the electron)
(easily gain
<
<
<
the electron)
4d NbO43 < MoO42 < TcO4
<
most powerful
<
<
oxidizing agent
5d TaO43 < WO42 < ReO4
poor oxidizing
agent
Dr. D. Suresh
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LEO = Loss of Electron, OXIDATION; Oxidation reagent undergo reduction
GER = Gain of Electron, REDUCTION; Reducing reagent undergo oxidation
88703 58876
186
Metal to ligand charge transfer (MLCT):
• Charge-transfer transitions from metal to ligand are observed when the
metal is in low oxidation state and the ligands have low-lying (*) acceptor
orbitals, especially aromatic ligands.
• MLCT transition occurs at low energy and appears in the visible spectrum if
• metal ion is in a low oxidation state,
• d orbitals are then relatively close in energy to the empty ligand
orbitals (*).
• MLCT results in oxidation of the metal
*
• MLCT most commonly occurs with ligands Ligand
eg * orbitals
having empty * orbitals, such as CO,
bipyridine.
Dr. D. Suresh O
Examples,
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Ni(CO)4, [W(CO)4(phen)], [Fe(CO)3(bpy)]
t2g
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2+ (biPy = 2,2’-bipyridine) 187
[Ru(bipy) 3]
Metal to ligand charge transfer (MLCT): *
eg
[Ru(bipy)3]2+
O
(biPy = 2,2’-bipyridine)
t2g
• The octahedral complexes [Ru(bipy)3]2+ (d6) MLCT bands.
• The bipyridine a strong ligands and having a low lying * orbital, which will
receive the electrons from the filled t2g orbital.
• Resulting in the formal oxidation of metal (via excitation from metal-based t2g
into orbitals with extensive * ligand character).
• Dr. D.complexes
These Suresh are used as “light-harvesting” materials and the redox
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properties of these ions facilitate electron transfer steps.
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Charge transfer in small molecule:
• The observed colors of the halogens arise from an * *

electronic transition from HOMO * to LUMO *.
• The HOMO–LUMO energy gap decreases in the order F2
> Cl2 > Br2 > I2, leading to a progressive shift in the
absorption maximum from the near-UV to the red region of
the visible spectrum.
• Dichlorine, dibromine and diiodine dissolve unchanged in
many non-polar (no donor) organic solvents (eg. hexane).

Halogens
• However, in ethers (O), ketones (O) and pyridine (N), which contain donor
Dr. D. Suresh
atoms, Br2 and I2 (and Cl2 to a smaller extent) form charge transfer
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complexes with the halogen *MO acting as acceptor orbital.
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Charge-Transfer Spectra CH3CN-I2
Charge transfer in small molecule:
• Solutions of I2 in donor solvents, such as
CH3CN:
pyridine, ethers or ketones, are brown or yellow.
• Even benzene acts as a donor, forming charge
transfer complexes with I2 and Br2.
* *
• Pyridines, ketones and similar compounds
donate electron density through a  lone pair,
benzene uses its -electrons and thereby
reduces the energy between * and *.

(donation electron stabilizes *)
• A UV-vis peak is arising from an electronic

transition from the solvent-X2 occupied
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bonding MO to a vacant antibonding MO.
sureshvnr@gmail.com C6H6-Br2 Halogens
• This
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is the58876
so-called charge transfer band.
Spin and Laporte Ligands (organic molecule)
allowed   * transitions
Charge transfer
Spin allowed
Laporte forbidden
Tetrahedral
All dd transtions
Spin allowed
Laporte forbidden
Octahedral
All dd transtions
Intensity
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Spin and Laporte forbidden
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(d5) ions
CSIR December 2015
GATE 2015
GATE 2007
GATE 2011
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CSIR December 2017
* *
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• When molecules absorb energy in the infra red region the vibrational
transition occurs.
• These transition give rise to a spectrum are called Vibrational spectroscopy
or IR spectroscopy.
• The interaction of IR radiation with molecules caused the excitation of

vibration levels in the molecules.
• Resulting in vibration of the bonds of the molecules.
V3
V2
V1
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Vo
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Infrared region
Region Range Origin of the absorption
Near Overtones and combination bands of
12500 - 4000 cm-1
IR fundamental molecular vibrations
Mid 4000 - 1300 cm-1
Fundamental molecular vibrations
IR 1300 – 650 cm-1
Far Bending vibrations of C, N, and heavier
650- 10 cm-1
IR atoms
• Near-infrared refers to the part of the infrared spectrum that is closest to

visible light and far-infrared refers to the part that is closer to the microwave
region.
• Mid-infrared is the region between these two. For chemical analysis, mid IR
region is widely used.
• Dr. D. Suresh
Radiation in the Mid IR region will cause stretching and bending vibrations of
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the bonds in most covalent molecules.
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Selection Rules
Selection rule:
• A molecule will absorb infrared radiation if the change in vibrational states is
associated with a change in the dipole moment () of the molecule.
 = qr
• q: electrical charge, r: directed distance of that charge from some defined
origin of coordinates from the molecule.
• Dipole moment is greater when electronegativity difference between the

atoms in a bond is greater. Some electronegativity values are:
H 2.2; C 2.55; N 3.04; O 3.44; F 3.98; P 2.19; S 2.58; Cl 3.16
• Dr. D. Suresh
Vibrations which do not change the dipole moment are Infrared Inactive
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(homonuclear diatomics).
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Selection Rules
• Molecule must have change in dipole moment due to vibration or rotation to
absorb IR radiation.
• Molecules with permanent dipole moments (μ) are IR active
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Vibrational modes in molecule
Vibration
Stretching mode Bending mode

Stretching Vibration
Symmetrical stretching:
• Simultaneous vibration of two bonds, in
which the bonds elongate together and
contract together
Asymmetrical stretching:
• Simultaneous vibration of two bonds, with
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opposite atomic motions. While one bond is
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elongating the other is contracting
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Bending Vibration
Deformation or Scissoring:
• The two atoms connected to central atom
move toward and away from each other
Rocking or in-plane bending:
• The structural units swings back and forth in

the symmetry plane of molecule.
Wagging or out-of-plane bending:
• The structural units swings back and forth in

the plane perpendicular to the molecule’s
symmetry plane
Twisting:
• The structural unit rotates back and forth
Dr. D. Suresh
around the bond that joins it to the rest of
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molecule.
Vibrational modes in molecule
Vibration
Stretching mode Bending mode
Symmetrical Asymmetrical
Deformation Rocking Wagging Twisting

Or Or Or
Scissoring in-plane bending out-of-plane bending
• Among the different types of vibrations, to stretch a bond asymmetrically,

more energy is required and hence the it has higher stretching frequency.
• Dr.order
The D. Suresh
of energy required is as follows,
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ν Asym  ν Sym  ν Bending
Only some modes may be IR active:
Example CO2 O=C=O linear
Symmetric stretching
Asymmetric stretching
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Factors to be considered in an IR spectrum
1) Position of absorbance (wavenumber) - Energy required for absorbance
2) Intensity of absorbance - Related to the dipole of the bond
3) Shape of absorbance (broad or sharp peaks) - Tells information about the
type of bond
Group region Finger print region
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Wavenumber of absorbance
Wavenumber of absorbance, ν can be calculated:
ν where
K = force constant-force required to stretch the bond

µ = reduced mass mA =mass of A atom; mB = mass of B atom
c = velocity of light
The wavenumber of absorbance is
indirectly to proportional the masses of the atoms in the bond
The stretching frequencies for bonds to carbon are as follows:
C-H > C-C > C-N > C-O
The wavenumber of absorbance is
directly proportional to the strength of the bond
The stronger the bond, the higher the vibrational frequency.
Dr. D. Suresh
C≡C > C=C > C-C; C≡N > C=N > C-N
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≡C-H > =C-H > -C-H
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C≡O > C=O > C-O; 203
Group frequencies
• Most groups of interest show characteristic frequencies of stretching vibrations
lie in the region 4000 to 1500 cm-1 and are called as the group frequency region.
• The presence of various group vibrations in the IR spectrum is of great
assistance in identifying the absorbing molecule.
Group region
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88703 58876 Finger print region 204
Fingerprint region
• The region from about 1500 to 400 cm-1 usually contains a very complicated
series of absorptions due to all manner of bending vibrations within the
molecule and referred as fingerprint region.
• No two unique molecular structures produce the same infrared spectrum.
This makes infrared spectroscopy useful for identification purpose by
comparison with library spectra.
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Fingerprint region
IR spectroscopy of Carbonyl (CO) Ligand
The energy necessary to stretch
a bond is equal to
k = force constant, a measure of strength of bond

 = reduces mass; for atoms of mass m1 and m2,
the reduces mass is given by
In conclusion,
• The stronger the bond between two atoms, the larger the force constant;
consequently, the greater the energy necessary to stretch the bond and the
higher the energy of the corresponding band that is the higher the wave
number ( , cm−1) in the infrared spectrum.
• Higher the mass of the atoms involved in the bond, higher will be the
Dr. D. mass
reduced Suresh
(), subsequently the less energy is necessary to stretch the
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bond that is the lower waver number ( , cm−1) in the IR spectrum.
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Group frequencies
• Organic molecules contain many atoms.
• As a result, there are many stretching and bending modes and the IR
spectrum has many absorption bands.
Four distinct regions of an IR spectra,
4000 cm-1 2500 cm-1 2000 cm-1 1500 cm-1 500 cm-1
=C-H; -N-H; -O-H CC; CN C=C; C=N;
CO C=O
Finger print
X-H
Double region
Single bond region Triple bond
bond region
region
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IR spectroscopy of Hydrocarbon Compounds
Wave number Shape/
Bond
(Cm-1) Intensity
-C-H  2850 - 2950 sharp, strong
=C-H  3000 -3100 sharp, strong
C-H  3310 - 3320 sharp, strong
-C-O 1025 - 1200 Sharp, strong
Bond Wave number (Cm-1) Shape/Intensity

C-C  1200 weak
C=C (isolate)  1640-1680 sharp, strong
C=C (Conjugate)  1620-1640 sharp, strong
Dr. (aromatic)
C=C D. Suresh  1600
sharp, strong
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CC58876  2100 - 2200 208
weak, often not observed
IR spectroscopy of Alcohols and Amines Compounds
Both O-H and N-H bonds are “stiff” bonds
Wave number
Bond Compound Shape/Intensity
(Cm-1)
-O-H R-OH (alcohol)  3200 - 3600 broad, strong
-O-H R-C(O)OH (acid)  2500 - 3600 very broad
-N-H R-NH2, (Primary amine)  3350 - 3500 broad, medium
R2NH (secondary amine)
Wave number
(Cm-1)
-S-H R-SH (thiol)  2590 - 2540 broad, weak
Wave number
(Cm-1)
-C-N amine  1180 - 1360 sharp, strong
Dr.
-C=N D. Sureshimine  1640 - 1690 sharp, strong
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-CN nitrile  2210 - 2280 sharp, strong
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IR spectroscopy of Carbonyl Compounds
One of the best diagnostic features of IR is for carbonyl compounds

Remember there are many types of carbonyl groups
(each can be differentiated only with an IR spectrum)
~1730 - 1740 ~1640-1680
C=O ~ 1715 - 1725

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C=O are sharp and very strong
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IR Spectroscopy of Inorganic Molecules
Dr. D. Suresh
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IR Spectroscopy of Inorganic Molecules
Typical ranges of fundamental stretching wavenumbers of selected groups
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Bonding mode and IR starching frequencies of CO ligands:
• Both σ donation (which donates electron density from a bonding orbital on

CO) and acceptance (which places electron density in CO anti-bonding
orbitals) would be expected to weaken the C−O bond and to decrease the
energy necessary to stretch that bond.
• The stretching frequency will be lower when it coordinated to metal than the
free CO gas.
Dr. D. Suresh
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Free CO > terminal CO > doubly bridging CO (μ2) > triply bridging CO213
(μ3)
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Bonding mode and IR starching frequencies of CO ligands:
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Electronegativities of metal and IR starching frequencies of CO ligands:
Metal Electro- ,CO

carbonyls negativity cm-1
V(CO)6 1.6 1976
Cr(CO)6 1.6 2000
Mn2(CO)10 1.6 2013
Fe(CO)5 1.8 2023
Co2(CO)8 1.9 2044
Ni(CO)4 1.9 2057 Higher the electronegativity of metal
decreases the back -bonding
• Higher the electronegativity of metal atom, do not favor the metal to donate
electrons to * orbital (weak back -bonding) of CO, and hence M-C bond is
Dr. D. Suresh
weakened and strengthened the C-O bond.
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• Hence higher the starching frequency for CO in IR spectrum.
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215
Charge on complex and IR starching frequencies of CO ligands:
• The charge on a carbonyl complex is also reflected in its infrared spectrum.
Complexes ,CO cm-1

Free CO 2143
[V(CO)6]- 1858
[Cr(CO)6] 2000
[Mn(CO)6]+ 2095 Negative charge (-ve) on metal

increases the back -bonding
• Higher the negative charge (-ve) on the complex, favors the metal to donate
electrons to * orbital (strong back -bonding) of CO, and hence M-C bond
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strengthened and weakens the C-O bond.
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• Hence lower the starching frequency of CO in IR spectrum.
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Charge on complex and IR starching frequencies of CO ligands:
Positive charge (+ve) on metal

decreases the back -bonding
• Higher the positive charge (+ve) on the complex, reduced the ability of metal
to donate electrons to * orbital (weaker back -bonding) of CO, and hence
Dr.bond
M-C D. Suresh
is weakened and strengthened the C-O bond.
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• Hence higher the starching frequency of CO in IR spectrum.
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217
• Charge on complex and IR stretching frequencies of CO ligands:
[Ti(CO)6]2- [V(CO)6]- [Cr(CO)6] [Mn(CO)6]+ [Fe(CO)6]2+

υCO 1748 1858 1984 2094 2204 cm-1
Increasing M=C double due to Decreasing M=C double due to

good –bonding which in turn poor –bonding which in turn
lowers the CO bond strength increased the CO bond strength
and have lower IR υCO and have higher IR υCO
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- donor ligands
Carbonyl ligand (CO):
Bond Distances:
• In free CO, the bond distance of C−O is 1.128 Å.
• Weakening of the C−O bond in carbonyl complexes by σ-donation and -
acceptance would be expected to cause this distance to increase (weaken
the C-O bond strength). Such an increase in bond length is found in
complexes containing CO, with C−O distances of approximately 115 pm for
many neutral carbonyl complexes.
• Although such measurements provide definitive measures of bond
distances, in practice it is far more convenient to use infrared spectra to
obtain data on the strength of C−O bonds.
Free CO Terminal CO 2-CO 3-CO

Dr.distance
Bond D. Suresh
(Å) 1.128 1.12 – 1.18 1.17 – 1.22 1.17 – 1.22
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, CO (cm-1) 2143 1850 - 2120 1750 - 1850 1620 -219
1730
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IR spectroscopy of Metal Carbonyls Complexes and Group Theory
Complex Point group Symmetries of IR Number
CO stretching active of IR
modes modes Peaks
Oh A1g, Eg, T1u T1u 1
[M(CO)6]
C4v A1, A1, B1, E A1, A1, B1 3
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[XM(CO) ] Presence of “g” indicates IR inactive mode
modes modes Peaks
D4h A1g, B1g, Eu Eu 1
trans-[X2M(CO)4]
C2v A1, A1, B1, B2 A1, A1, B1, B2 4

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cis-[X2M(CO)4] Presence of “g” indicates IR inactive mode
modes modes Peaks
C3v A1, E A1, E 2
fac-[L3M(CO)3] Presence of “g” indicates IR inactive mode
C2v A1, A1, B1 A1, A1, B1 3
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mer-[L3M(CO)3]
88703 58876 Presence of “g” indicates IR inactive mode
Geometry and Group Theory
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IR spectroscopy of Metal carbonyls in presence of phosphine ligands
IR spectroscopy of Metal carbonyls in presence of phosphine ligands:
R = Electron releasing group R = Electron withdrawing group
• Better -donor and poor -acceptor • Poor -donor and good -acceptor
• As a result, weaker M-P bond. • As a result, stronger M-P bond.
• Hence, M-C stronger, in turn C-O • Hence, M-C weakened, in turn C-O
bond is weakened. bond is strengthened.
• So, lowest CO stretching frequency. • So, highest CO stretching
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R = Electron releasing group:
When, R = electron  -Bond  -Bond
releasing group, * back donation * back donation
favours this
Carbonyl ligand Phosphine ligand

Metal
Typically, it looks like, O=C=M-P(R)3; R = electron releasing group
• Phosphines acts as better -donor and poor -acceptor
• As a result, weaker M-P bond is formed.
Dr. D. Suresh
• Resulting in stronger M-C bond which in turn weakens the C-O bond.
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• Thus, lowest CO stretching frequency.
R = Electron withdrawing group: When, R = electron
 -Bond  -Bond withdrawing group,
* back donation * back donation favours this
Carbonyl ligand Phosphine ligand

Metal
Typically, it looks like, OC-M=P(R)3; R = electron withdrawing group
• Phosphines acts as poor -donor and very good -acceptor
• As a result, strong M-P bond is formed.
Dr. D. Suresh
• Resulting in weaker M-C bond which in turn strengthened the C-O bond.
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• Thus, higher CO stretching frequency.
Increase in the
Increase in C-O
electron
stretching
withdrawing
frequency
power on P
• Increase in the electron withdrawing power on P atom favours the back –

bonding and strengthen the M-P bond.
• Subsequently weakens the M-C bond which in turn increases the C-O bond
Dr. D. Suresh
strength and hence higher stretching frequency in IR.
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• Going down the series of complexes in

this table, the -donor ability of the
phosphine ligands increases and the -
acceptor ability decreases.
• PF3 is the weakest -donor (due to highly electronegative of fluorines) and

the strongest -acceptor.
• Conversely, PMe3 is the strongest -donor and the weakest -acceptor.
• As a result, the molybdenum in Mo(CO)3(PMe3)3 carries the greatest
electron density; it is the most able to donate electron density to the *
orbitals of the CO ligands.
• Dr. D. Suresh
Consequently, the CO ligands in Mo(CO)3(PMe3)3 have the weakest C-O
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bonds and the lowest energy stretching bands.
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IR spectroscopy of Metal Nitrosyl Complex
• Distinction between the two coordination modes (linear and bent) can be
identified using IR spectroscopy.
• In general, bent NO has a lower IR frequency than linear NO.
Terminal NO
Free NO Bridging NO
Linear Bent
, NO (cm-1) 1870 1620 – 1830 1520 – 1720 1400 – 1550
Bond angle M-N-O () 180 165 – 180 119 – 140 180
Formal charge = +1 Formal charge = 1
sp hybridization sp2 hybridization
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IR spectroscopy of Metal Nitrosyl Complex
• NO ligand can show terminal or bridging mode of coordination.
IR data for NO: NO terminal 1672 cm-1

NO bridge 1505 cm-1
Bent geometry
Linear geometry
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IR spectroscopy Metal Cyanide Complex
Cyanide (CN-):
• Cyanide can coordinate through N (cyanato) to the metal centre (M-N).
• The free CN gives stretching frequency at 2080 cm-1.
• When coordinated to metal atom, it can vary from 2200 – 2000 cm-1.
CN stretching frequency dependency: Presence of –ve charge in the

• Depends on ligand weakens the CN
(i) Electroneagativity (ii) Oxidation state (iii) coordination number

Electronegativity:
• Higher the electronegativity of the metal, higher the stretching frequency of
CN. (due to strong -bonding through negative charge, poor -back
bonding)
Complex CN (cm-1)
[Ni(CN)4] 2- 2150
Electronegativity
Dr. D. Suresh
increased [Pd(CN) ]2- 2143 Stretching frequency
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increased
[Pt(CN)4] 2128
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IR spectroscopy Metal Cyanide Complex
CN stretching frequency dependency:
Oxidation state:
• Higher the oxidation state of the metal, higher is the stretching frequency of
CN. (due to strong -bonding through negative charge, poor -back
bonding) Stretching
Complex Oxidation state CN (cm-1) frequency
Oxidation state
[V(CN)6]5- +1 1910 increased
increased
[V(CN)6]4- +2 2065
[V(CN)6]3- +3 2077
Coordination number:
• Higher the coordination number (decreases the positive charge on metal
centre) of a complex, lower is the stretching frequency of CN.
Coordination number Complex CN (cm-1) Stretching frequency

decreased increased
[Ag(CN)4]3- 2092
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3
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[Ag(CN)2]2- 2135
IR spectroscopy Metal Urea Complex
Urea:
• In case of Urea, both N and O can coordinate to metal centre.
• This can be easily identified using IR spectroscopy.
• When the coordination is through O, the C=O stretching frequency will
decreased which in turn increased the CN stretching frequency.
• If it coordinate through N atom the there will be a decrease in CN stretching
frequency and hence a increase in C=O stretching frequency.
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IR spectroscopy Metal-DMSO Complex
DMSO:
• Dimethyl sulfoxide, DMSO, can coordinate through both S and O atom to
metal centre. This can be easily identified using IR spectroscopy.
• When the coordination is through O, the S=O stretching frequency will
decreased.
• If it coordinate through S atom the there will be a increase in S=O stretching
frequency.
• Most of I row transition metal prefers O mode of coordination while II and III
row prefers S mode of coordination.
The free S=O stretching frequency comes around 1000 – 1500 cm-1
Dr. D. Suresh
 M M
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Introduction to NMR Spectroscopy
• Nuclear magnetic resonance (NMR)
spectroscopy is a powerful analytical
technique used to characterize the
chemical compounds.
• The source of energy in NMR is radio
waves which have long wavelengths, and
thus low energy and frequency.
• When low-energy radio waves interact
with a molecule, they can change the
Dr. D.spins
nuclear Suresh
of some elements, including
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1H and 13C.
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Theory of Nuclear Magnetic Resonance
• When a charged particle such as a proton spins on its axis, it
creates a magnetic field.
• Thus, the electron can be considered to be a tiny bar magnet.
• Generally, these tiny bar magnets are randomly

oriented in space.
• However, in the presence of an external

magnetic field H0, they can oriented with or
against the applied field. (Zeeman Effect)
• More electron are oriented with the applied

field because this arrangement is lower in
Dr. D.
energy.Suresh
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• The energy difference between these two states is very small (<0.1 cal)
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• charged particle spins on its axis and creates a
magnetic field and acts like a tiny bar magnet
E nucleus aligned
against H0 Ms = =- 1/2
E = h = µH0/I
nucleus aligned Ms = +1/2

with H0
Ms = electron spin
External magnet quantum number
with field H0
• Now two energy states for a electron: a lower energy state with the electron
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aligned in the same direction as H0, and a higher energy state in which the
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237
electron
• When an external energy source (h) that matches the energy difference
(E) between these two states is applied, energy is absorbed, causing the
nucleus to “spin flip” from one orientation to another.
H0
• The energy difference between these two nuclear spin states corresponds to
radiofrequency region of the electromagnetic spectrum.
Dr. D. Suresh
• A nucleus is in RESONANCE when it absorbs radiofrequency radiation and
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spin flips to a higher energy state
I = - 1/2
E = h = µH0/I
I = + 1/2
µ – magnetic moment of nucles; H0 – External magnetic field

I- Spin quantum number;  - frequency of radio wave
• The frequency need for resonance and the applied magnetic field strength
are directly proportional to each other.
• Larger the applied external magnetic field (H0), greater the energy difference
Dr. between
(E) D. Suresh
the two states, higher the radio frequency () needed for
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resonance
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NMR Active Nuclei
Conditions for atom to respond to NMR spectroscopy:
Mass Atomic Spin quantum number
number number (I)
Odd Odd or even 1/2 NMR active; 3/2; 5/2 NQR active)
Even Even 0 (NMR inactive)
Even Odd 1, 2, 3 (NQR active)
NQR = Nuclear Quadrupole Resonance
NQR transitions of nuclei can be detected
in the absence of a magnetic field
NMR inactive
NMR and NQR active
Dr. D. Suresh NMR active

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NMR active nuclei and their abundance
H0
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Information from NMR spectra
1. Number of signals
2. Position of signals (chemical shift)
3. Relative areas under signals (integration)
4. Splitting pattern
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1H NMR for Inorganic complexes
• Proton nuclear magnetic resonance (proton NMR, hydrogen-1 NMR, or 1H

NMR) is the application of nuclear magnetic resonance in NMR
spectroscopy with respect to hydrogen-1 nuclei within the molecules of a
substance, in order to determine the structure of its molecules.
• In samples where natural hydrogen (H) is used, practically all the hydrogen
consists of the isotope 1H (hydrogen-1; i.e. having a proton for a nucleus).
• The natural abundance of this isomer is 100% and has a spin value (I) of 1/2
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I = - 1/2
E = h = µH0/I
I = + 1/2
µ – magnetic moment of nuclear

H0 – External magnetic field
H0 I- Spin quantum number
I = + 1/2
Dr. D. Suresh
I = - 1/2
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Selection Rule
• In NMR, the selection rule refers to the spin quantum number m; only
transitions in which m changes by one (up or down) are allowed.
• This is sometimes expressed as,
m = m(initial state) - m(final state) = ± 1.
• Another way of saying this is that one spin can flip between 'up' and 'down'
or vice versa.
• In the case of spin a single spin-half, the change in m between the two
Dr. D. Suresh
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states is [(+1/2) - (-1/2)] = 1, so the transition is allowed.
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• In a compound, the protons are bonded to other atoms and so there are
more electrons in the region of the protons.
• These electrons affect the external magnetic field experienced by the proton.
• The energy gap between high- and low-energy states will be slightly
different.
• The frequency of radiation emitted as the nuclei relax back to the low-energy
state will also be different.
• Protons emitting radiation of the same frequency are said to be in the same
proton environment.
• Four different features of a 1H NMR spectrum provide information about a

compound’s structure:
Dr. D. Suresh
(1) Number of signals; (2) Position of signals;
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Intensity of signals; (4) Spin-spin splitting of signals
• Four different features of a 1H NMR spectrum provide information about a
compound’s structure:
a. Number of signals
b. Position of signals
c. Intensity of signals
d. Spin-spin splitting of signals
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Number of signals:
How many different types of nuclei in the molecule.
Position of signals (chemical shift):

What types of nuclei.
• The relative position of absorption in the NMR spectrum the chemical shift.
It is a unit less number, but we assign ‘units’ of ppm or  (delta) units.
• The scale varies with the nuclei of interest. (1H, the usual scale is 0 to 10
ppm (or ) and for 13C scale goes from 0 to about 220 ppm.
Relative areas under signals (integration):

How many nuclei of each type
Dr. pattern:
Splitting D. Suresh
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How many neighboring nuclei present
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1H NMR—Number of Signals:
• In a molecule, protons in the same magnetic environment absorb at the
same applied magnetic field strength, Ho; different environment – different
Ho.
• Equivalent protons give the same NMR signal where protons in different
environments give different NMR signals.
• Therefore, the number of NMR signals equals the number of different types
of protons in a molecule.
• A set of protons with the same magnetic environment are called as
magnetically equivalent protons.

Dr. D. Suresh
• Often, magnetically equivalent protons are chemically equivalent
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1H NMR—Number of Signals:
• Chemically equivalent protons are protons that are in the same chemical
environment, and they must be identical in every way.
• They experience the same magnetic force, and therefore, will create
overlapping signals on the spectrum.
• Therefore, we can determine how many sets of equivalent protons there are
in a molecule by looking at the number of signals in its 1H-NMR spectrum.
1-Signal 2-Signals 3-Signals

M M M
Dr. D. Suresh
1-Signal 2-Signals 3-Signals
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Finding of Chemically Equivalent Protons
• Look at the atom (usually a carbon) attached to the hydrogen and observe
what that atom is bonded to, and then the atom bonded to that, all the way
until a difference is observed.
• If there is no difference, the protons are equivalent. If there is a difference,
the protons are not equivalent.
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• In comparing two H atoms on a ring or double bond, two protons are
equivalent only if they are either cis (on same side) or trans (on opposite
side) to the same groups.
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CH3CH2-Br CH3CHCH2CH3 Cl-CH2CH2CH2-Cl

Br
two
four two
Cl-CH CH3
CH 2CH32CH2-Cl
3CHCH
CH2Cl
CH3ClCHCH2CH3 Cl-CH2CH2CH2-Cl
Br
two
two
CH3 three
H3four
CDr.CD.CH
Suresh
3
CH3CHtwo
2-Br
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2Cl Br 254
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1H NMR—Position of Signals
Shielding and Deshielding of protons:
• Under the influence of the applied magnetic field, electrons surrounding a
nucleus start to circulate perpendicular to the applied magnetic field H0, and
so they generate a secondary magnetic field called induced magnetic field
(H0) opposes the applied magnetic field in the region of the nucleus.
• Thus, the nucleus experiences a weaker magnetic field (Heff) than the
applied magnetic field H0, and it is said to be shielded.
• This type of shielding is termed diamagnetic and its effect is termed as
shielding effect.
H o)
Dr. D.H Suresh

o Ho Heff= Ho  Ho
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• If due to some reason, the electron density around proton get reduced, then
the proton is said to be deshilded.
• Basically, an electron withdrawing group removes the electron density of the
protons and are thus deshielded.
• While the electron releasing group adds the electron density and hence the
they are shielded more.
H o)
Heff= Ho  Ho Heff = Ho  Ho;

Ho Ho
 = shielding constant
Dr. D. Suresh
Ho
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 = shielding constant; Increases when electron releasing group is present 256
88703 58876 Decreases when electron withdrawing is present
• The shielded protons feel less applied magnetic field (H0) and hence the
energy separation is low and hence a lower frequency of radio wave is
sufficient to excite this proton.
• Whereas the deshielded protons feel high applied magnetic field (H0) and
hence the energy separation is high and hence a higher frequency of radio
wave is needed to excite this proton. h = E = H0/I
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Shielding and Deshielding are relative terms
Less More
Electron density Electron density
Deshielded
protons TMS
Shielded
standard
protons
aromatic,
Ketone, aliphatic
aldehyde,
acid,
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10 Chemical shift, ppm 0
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258
Shielding and Deshielding are relative terms
Less More
Electron density Electron density
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பால்: அறத்துப்பால் அதிகாரம்: பசய்ந்நன்றி அறிதல் குறள்: 105
உதவி ைவரத்தன்று உதவி உதவி
சசயப்பட்டார் சால்பின் ைவரத்து
• ஒருைர் நமக்குச் சசய்த உதவிக்குத் திரும்ப நாம் சசய்ைது, அைர்
சசய்த உதவியின் காரணம், சபாருள், காலம் பார்த்து அன்று;
உதவிவயப் சபற்ற நம் பண்பாட்டுத் தகுதியய அதற்கு அைைாகும்.
Translation:
• The kindly aid's extent is of its worth no measure true;
• Its worth is as the worth of him to whom the act you do.
Explanation:
• Dr.benefit
The D. Suresh
itself is not the measure of the benefit; the worth of those who
have received it is its measure.
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Typical Values of 1H NMR Chemical Shift
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1H NMR—Position of Signals:
Protons Chemical shift
M-H – 5 to – 20
M-CH3 1 to 4
M-Olefin  3 to 4
M- (C5H5) (Cp)  4
M-(C6H6)  4 to 7
M=CH2  10
• Protons bonded directly to metals, metal hydrides (M-H), are very strongly
shielded, with chemical shifts commonly in the approximate range of –5 to –
20 ppm relative
• Protons in methyl complexes (M-CH3) typically have chemical shifts between
1 and 4 ppm.
Dr. D. Suresh
• Cyclic  ligand like 5-C5H5 and 5-C6H6, most commonly have 1H chemical
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shifts between 4 and 7 ppm.
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Intensity of signals
• In 1H spectrum, the area under each peak (the intensity of the peak) is
directly proportional to the number of protons causing that peak.
• Greater the number of protons which flip over at a particular frequency,
greater is the energy absorbed and greater is the area under the absorption
peak.
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Spin-Spin Splitting of Signals
• Spin-spin splitting of signals into several peaks (multiplets) showing the
environment of a proton with respect to the neighboring protons
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Spin-Spin Splitting of Signals
• Spin-spin splitting occurs only between non-equivalent protons on the same

carbon or adjacent carbons.
• Non-equivalent protons on adjacent carbons have magnetic fields that may

align with or oppose the external field.
• This magnetic coupling causes the proton to absorb slightly downfield when
the external field is reinforced and slightly upfield when the external field is
opposed.
• All possibilities exist, so signal is split.

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1H NMR—Spin-Spin Splitting
Ho
Ho Ho
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-CH2-CH3
-CH2 Resonance -CH3 Resonance

Quartet (1:3:3:1) Triplet (1:2:1)
= nuclear orientation
(1) (1)
aligned non-aligned
(1) (1)
aligned non-aligned
(3) (3) (2)
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reinforced reinforced
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Spin states of neighbouring Spin states of neighbouring
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CH3 protons CH2 protons
• Rules describe the splitting patterns commonly seen in the 1H NMR spectra
of organic compounds.
1. Equivalent protons do not split each other’s signals.
2. Protons separated by a maximum of three bonds will split.
3. Splitting is observed for non-equivalent protons on the same carbon or
adjacent carbons.
4. A set of “n” non-equivalent protons splits the signal of a nearby proton into
n + 1 peaks in 1H NMR.
No. of splitting peak = 2nI + 1 (I = ½ for 1H, 13C)
For 1H and 13C No. of splitting peak = n + 1 (I = ½ for 1H, 13C)

If Ha and Hb are not equivalent, splitting is observed when,
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The N + 1 Rule
If a signal is split by N equivalent protons, it is split into N + 1 peaks.
Singlet Doublet Triplet Quartet Quintet Sextet Septet Octect

0 adj H 1 adj H 2 adj H 3 adj H 4 adj H 5 adj H 6 adj H 7 adj H
1 1:1 1:2:1 1:3:3:1 1:4:6:4:1 1:5:10:10:5:1 1:6:15:20:10:6:1 1:7:21:35:35:21:7:1
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Coupling Constants:
• Distance between the

peaks of multiplet and
measured in Hz
• Not dependent on strength
of the external field
Values for Coupling Constants:
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Characteristic nature of coupling constant J:
• The magnitude of J measures how strongly the nuclear spins interact with
each other.
• Coupling is normally a through-bond interaction, and is proportional to the
product of the gyromagnetic ratios of the coupled nuclei.
• Spin-spin interactions are independent of the strength of the applied field.
• Since coupling occurs through chemical bonds, the magnitude of J normally
falls off rapidly as the number of intervening bonds increases. For example,
1J ~700 while 2JPH ~20 Hz

PH
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CSIR December 2014
CSIR June 2015
• InDr.
“A” D.
DueSuresh
to good pi back bonding, all the electrons are moved towards the
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CO and leave the Cp more deshieded
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(CH3CH2O)4Si
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13C NMR
• Carbon exhibit two isotopes 12C and 13C
• 12C does not exhibit NMR behavior (I=0) while 13C (I= 1/2) has only about
1.1% natural abundance (of carbon atoms).
• 13C nucleus is about 400 times less sensitive than 1H nucleus to the NMR
phenomena. Due to the low abundance, usually see 13C-13C coupling is not
observed.
• Chemical shift range is normally 0 to 220 ppm
• Chemical shifts are measured with respect to tetramethylsilane, (CH3)4Si (i.e.
TMS)
• Similar factors affect the chemical shifts in 13C as seen for 1H-NMR
• Long relaxation times (excited state to ground state) mean no integrations.
Dr. D. Suresh
"Normal" 13C spectra are "broadband, proton decoupled" so the peaks show
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as single lines. Number of peaks indicates the number of types of C
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13C NMR
I = - 1/2
E = h = µH0/I
I = + 1/2
µ – magnetic moment of nuclear

H0 – External magnetic field
H0 I- Spin quantum number
I = + 1/2
Dr. D. Suresh
I = - 1/2
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Proton Spin Decoupling
Spin-Spin Splitting:
• It is unlikely that a 13C would see another 13C, so splitting by carbon is
negligible (due to low aboundance).
• However, 13C will magnetically couple with attached protons and adjacent
protons.
• These complexity in splitting patterns made difficult to interpret.
Proton Spin Decoupling:
• In "normal" 13C spectra, these couplings are "removed" by applying a

continuous second radio frequency signal of a broad frequency range that
excites all the H nuclei and cancels out the coupling patterns due to the
interaction of the H with the 13C.
• This means that each carbon is seen as a single line.
• Of Dr. D. Suresh
course information is being lost by doing this, such as how many H are
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attached to each C.
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13C NMR Spectrum
• Features of a 13C NMR spectrum provide information about a compound’s

structure:
Information provided
Presence of non-protonated carbons

• via small (weak) signals
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13C NMR for Inorganic complexes
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Predicting 13C{1H} Spectra
O OCH2
CH3COCH2CH3 CH3
CH3
CDCl3 (solvent)
O
C
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O
CH3CH2COCH2CH3
CH3
OCH2
CH2
CDCl3 (solvent) CH3
O
C
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O
CH3CCH2CH3 CH3
CH2
CH3
O CDCl3 (solvent)
C
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H
C H
C C
C C
H C H CH3
O H
CDCl3 (solvent)
C
expanded below
H H
O
CH3C H C C
C
H H
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CH2
CH3
CH2 Br
CH3CH2CH2Br
CDCl3 (solvent)
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CH2
CH3CH2CH2OH CH3
CH2 OH
CDCl3 (solvent)
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CH2
CH2
CH3
CH2 OH
CH3CH2CH2CH2OH
CDCl3 (solvent)
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CH2
CH2 CH2
CH3CH2CH2CH2CH2OH CH2 OH CH3
CDCl3 (solvent)
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CH3
C H
C
C
CDCl3 (solvent)
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CH2
C
CH3 CH2CH2CH2CH3
.
2-methyl-1-hexene
CH2
CDCl3 (solvent)
CH2
CH2
CH3
CH3
CH2
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பால்: பபாருட்பால் அதிகாரம்: இரவச்சம் குறள்: 1063
இன்வம இடும்வப இரந்துதீர் ைாசமன்னும்
ைன்வமயின் ைன்பாட்ட தில்.
• இல்லாவமயால் ைரும் துன்பத்வத (உவைத்துப் யபாக்காது) பிச்வச
எடுத்துப் யபாக்கிக் சகாள்ைலாம் என்று எண்ணும் சகாடுவமயிலும்
சகாடுவம யைறு இல்வல.
Translation:
• Nothing is harder than the hardness that will say,
• 'The plague of penury by asking alms we'll drive away'
Explanation:
• All that has been obtained with tears (to the victim) will depart with tears (to
Dr. D. Suresh
himself); but what has been by fair means; though with loss at first, will
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afterwards yield fruit.
Dr. D. Suresh
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13C NMR Spectrum
• Features of a 13C NMR spectrum provide information about a compound’s

structure:
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19F NMR for Inorganic complexes
• 19F has an I value of 1/2 and it is NMR active with 100% abundance.
• Chemical shift value ranges from - 900 ppm to + 900 ppm.

• Not easy to interpret.
• Sensitive to electronegativity and oxidation state of the neighbouring group
to stereochemistry.
• CFCl3 was used as external standard, (TMS = Internal standard in 1H).
Number of peaks determination in inorganic compounds:
• The inorganic compounds are always represented with molecular formula
not with structural formula.
• For predicting the signal it is mandatory to find the geometry and structural
formula
• The first step is to identify the geometry and shape using VSEPR theory.
Dr. D. Suresh
• Based on that number of signal is obtained.
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the splitting pattern 300
Chemical Shift values
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VSEPR Theory
Perfect Geometry
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302
VSEPR Theory
Deviations from regular geometry (Shapes)
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VSEPR Theory
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VSEPR Theory
Bonding pairs Lone pairs Shape
7 0 Pentagonal bipyramidal
6 1 Distorted octahedral
5 2 Pentagonal planar
4 3 Distorted square planar
3 4 T-shape
2 5 bent
Finding Geometry/shape using VSEPR Theory:
Step: 1 Calculate the total valence electron
Step: 2 Find the total number of bonded electrons (TBE)
One A-B contains 8 electrons
For H containing molecules, A-H contains two electrons
Bonding pairs = TBE/2
Step: 3 Calculate the number of lone pairs of electrons.
Dr. D. Suresh
Lone pair of electron = (TVE – TBE) / 2
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Step: 4 Find the shape/geometry according the bonding pairs and lone 305
pairs
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VSEPR Theory:
(Shapes)
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Number of peaks determination: ClF3
Step 1: To determine the shape and geometry
• Total valence electron (TVE) = 7 + (3  7) = 28 electrons

• 3 F is bonded to chlorine so by octet rule it should contain (3  8) 24
electrons. That is the total bonded electron (TBE).
• Lone pair of electron is give by (TVE – TBE) / 2.
• That is 28 - 24/2 = 2; so two lone of pair of electrons.
• Hence the molecule contains 3 bonded pair and 2 lone pairs (total is 5 pairs,
so it should deviate from TBP) , so the structure is T shape.
• Two different F and two signals.

• These two couple each other (2nI + 1) and
Dr. D. Suresh give rise to doublet and triplet with the

sureshvnr@gmail.com intensity of 2 and 1, respectively.
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Number of peaks determination:
ClF5
• That is 42 - 40/2 = 1; so one lone of pair of electrons.
• Hence the molecule contains 5 bonded pair and 1 lone pair (total is 6 pairs,
so it should deviate from octahedral), so the structure is square pyramidal.
• These two couple each other (2nI + 1) and give
Dr. D. Suresh rise to doublet and quintet with the intensity of 4

sureshvnr@gmail.com and 1, respectively.
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Dr. D. Suresh
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ClF - singlet BeF2 - singlet
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Compounds Number of signals

WF6 1
Only one signal
WF5Cl 1
trans-WF4Cl2 1
cis-WF4Cl2 1
fac-WF3Cl3 1
mer-WF3Cl3 2
trans-WF2Cl4 1
cis-WF2Cl4 1
WFCl5 1
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GATE 2008
GATE 2016
GATE 2016
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31P NMR for Inorganic complexes
• 31P has an I value of 1/2 and it is NMR active with 100% abundance.
• Chemical shift value ranges from -250 ppm to + 250 ppm.

• H3PO4 was used as external standard, (TMS is used as internal standard in
1H)
• The phosphorous element (P4) shows a peak at –460 ppm.
• The chemical shift of trivalent phosphorous, P(III) derivatives (PR3), are
strongly depends on the substituent.
• However the pentavalent P(V) are not depends on the substituents and
ranges from – 50 to 100 ppm.
•
Dr. D. Suresh
Based on that number of signal is obtained.
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Dr. D. Suresh
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Phosphorous (III) compounds
Phosphorous (V) compounds
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31P NMR of P4S3 shows two peaks.

One is doublet with intensity 3 and a quartet with intensity 1.
2 signal
Doublet with intensity 2
Dr. D. Suresh 1 signal Triplet with intensity 1
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1 signal
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mer-[Cl 58876
3Ir(PPh 3)3]
fac-[Cl3Ru(PPh3)3] mer-[Cl3Ru(PPh3)3]
• In case of meridonal isomer the P

• In case of facial isomer, all the P
ligands are in two different
ligands are equivalent.
environment. (2P are trans to one
• Hence, only one signal in 31P NMR.
another and 1P is trans to Cl)
• Hence, two signal in 31P NMR.
• Due to coupling, they appear as
Dr. D. Suresh
Similarly cis- and trans isomer
doublet with intensity 2 and triplet
can also be distinguished
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with intensity 1.
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GATE 2008
CSIR June 2012
Dr. D. Suresh
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10 and 11B NMR for Inorganic complexes
• Boron has two naturally occurring NMR active nuclei 10B and 11B.
• Both nuclei have spins of greater than ½ and are quadrupolar.
• 11B has a spin of (I) 3/2 and 10B is spin (I) 3.
• 11B is the better nucleus in all respects, having the lower quadrupole
moment and being more sensitive.
• The chemical shift ranges from 100 to -150 ppm.
• Et2O·BF3 is used as external standard
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BF3
• BF3 is planar. Also only one B is there, so only one signal
• NMR sample tube is made of

borosilicate glass, hence it
also shows some peak
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• Boron usually coupled with hydrogen attached directly to it.
• Thus it is very helpful in predicting the structure of boranes, carboranes.
• Example, B10H14,
Dr. D. Suresh
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Over view of NMR Spectroscopy
1H 13C 19F{1H} 31P{1H} 11B{1H}
Abundance (%) 100 1 100 100 100

I 1/2 1/2 1/2 1/2 3/2
Standard CDCl3 CDCl3 CFCl3 H3PO4 F3B:OEt
(internal) (internal) (external) (external) (external)
No. of signals Yes Yes Yes Yes Yes
- 20 to 0 to - 900 to - 250 to - 100 to
Chemical shift
+ 20 + 200 -+ 900 + 250 + 150
Integration Yes No Yes Yes Yes
Spin-spin Yes, but Yes, but Yes, but
Yes No
coupling not for 1H not for 1H not for 1H
Dr. D. Suresh
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NMR for Inorganic complexes
Heteronuclear spin–spin coupling:
• When a molecule containing more than one NMR active nuclei, it tend to
couple each other and giving more information about the environment.
Coupling to spin-1/2 isotopes of 100% abundance:
Dr. D. Suresh
• The interaction between two spin-1/2 nuclei of both having 100% abundance
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results in a splitting of both resonances.
Number of peaks determination: PF5
• That is 40 - 40/2 = 0; so zero one lone of pair of electrons.
• Hence the molecule contains 5 bonded pair and 0 lone pair (total is 5 pairs),
so the structure is trigonal pybiramidal.
• These two couple each other (2nI + 1) and give rise to
triplet and quartet with the intensity of 3 and 2,
respectively.
Dr. D. Suresh
• These two peaks further coupled with 31P (I = 1/2;
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100%) to give triplet of doublet and quartet of doublet
2nI + 1 2nI + 1
231/2 +1 = 4 F-F 221/2 +1 = 3 F-F
2nI + 1 2nI + 1
211/2 +1 = 2 F-P 211/2 +1 = 2 F-P
quartet of doublet triplet of doublet
• When two or more nuceli are interacting, then the number of splitting lines
are given by
(2naIa + 1) (2nbIb + 1)... na,b = number of equivalent nuclei of A and B
Ia,b = nuclear spin of A and B
For Dr.
F, D. Suresh For F,
= (2(3)F(1/2)F + 1)  (2(1)P(1/2)P + 1)
sureshvnr@gmail.com = (2(2)F(1/2)F + 1)  (2(1)P(1/2)P + 1)
= 4  2 = 8 lines 325
88703 58876 = 3  2 = 6 lines
Number of peaks determination: PF3Cl2
• Total valence electron (TVE) = 5 + (3  7) + (2  7) = 40 electrons
• 3 F and 2 Cl is bonded to chlorine so by octet rule it should contain (5  8)
40 electrons. That is the total bonded electron (TBE).
• That is 40 - 40/2 = 0; so zero one lone of pair of electrons.
• Hence the molecule contains 5 bonded pair and 0 lone pair (total is 5 pairs),
so the structure is trigonal pybiramidal.
• These two couple each other (2nI + 1) and give rise
to triplet and double with the intensity of 1 and 2,
respectively.
Dr. D. Suresh
• These two peaks further coupled with 31P (I = 1/2;
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100%) to give triplet of doublet and doublet of doublet
2nI + 1 2nI + 1
221/2 +1 = 3 F-F 211/2 +1 = 2 F-F
2nI + 1 2nI + 1
211/2 +1 = 2 F-P 211/2 +1 = 2 F-P
triplet of doublet doublet of doublet
are given by
For Dr.
F, D. Suresh For F,
= (2(2)F(1/2)F + 1)  (2(1)P(1/2)P + 1)
sureshvnr@gmail.com = (2(1)F(1/2)F + 1)  (2(1)P(1/2)P + 1)
= 3  2 = 6 lines 327
88703 58876 = 2  2 = 6 lines
In 31P NMR spectrum:
PCl3 FPCl2 F2PCl F3P
Other than 31P three active

two active NMR
no other active one active NMR NMR nuclei, 19F
nuclei, 19F
NMR nuclei nuclei, 19F = (2nI + 1)
= (2nI + 1)
= (2nI + 1) = (2nI + 1) = (2  2  1/2) + 1 = (2  3  1/2) + 1
= (2  3  0) + 1 = (2  1  1/2) + 1 =3 =4
=1 =2
singlet
inactive NMR doublet
nuclei, I = 0
Dr. D. Suresh triplet
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PR3
all are pyramidal shape
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quartet
In 19F NMR spectrum:
PCl3 FPCl2 F2PCl F3P
No 19F, hence
no signals
Chemical shift and coupling constant will vary
Other than 19F, Other than 19F, Other than 19F,

PR3 one 31P NMR
one 31P NMR one 31P NMR
all are active nuclei
active nuclei active nuclei
pyramidal
shape
Dr. D. Suresh
= (2nI + 1) = (2nI + 1) = (2nI + 1)
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= (2  1  1/2) + 1 = (2  1  1/2) + 1 = (2  1  1/2) + 1
=2 =2
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=2
பால்: பபாருட்பால் அதிகாரம்: நல்குரவு குறள்: 1043
சதால்ைரவும் யதாலும் சகடுக்கும் சதாவகயாக
நல்குரவு என்னும் நவச
• ஒருைனுக்கு ைறுவமயின் காரணமாகப் யபராவச
ஏற்படுயமயானால், அது அைனுவடய பரம்பவரப்
சபருவமவயயும், புகவையும் ஒரு யசரக் சகடுத்துவிடும்.
Translation:
• Importunate desire, which poverty men name,
• Destroys both old descent and goodly fame.
Explanation:
• Dr. D. Suresh
Hankering poverty destroys at once the greatness of (one's) ancient descent
and (the dignity of one's) speech.
88703 58876
100% abundant NMR nuclei Less abundant NMR nuclei

a. Number of signals a. Number of signals
b. Position of signals b. Position of signals
c. Intensity of signals c. Intensity of signals
d. Spin-spin splitting of signals d. Spin-spin splitting of signals
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88703
• Then 58876 pattern
the splitting
Heteronuclear spin–spin coupling:

• When a molecule containing more than one NMR active nuclei, it tend to
couple each other and giving more information about the environment.
Dr. D. Suresh
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In 31P{1H} NMR spectrum
In 19F{1H} NMR spectrum
septet
doublet
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In 1H NMR spectrum
PR3 = pyramidal
For example, HPCl2
• The 1H NMR spectrum of HPCl2 shows a
doublet, this is due to the coupling
between H and P (both are NMR active
nuclei; I values for both nuclei are 1/2)
For example, HF2 ([F--H--F]):
• The 1H nucleus, but it is coupled to two chemically
= (2nI + 1)
equivalent 19F (I = 1/2) nuclei.
= (2  2  1/2) + 1
• By applying the spin-spin coupling rule (2nI + 1), a =3
n=2
triplet is appeared in the 1H NMR spectrum. (two fluorine atoms)
1H nuclei in absence of 19F
Dr. D. Suresh 1H nuclei coupled with first 19F
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1H 334
nuclei coupled with second 19F
HF2 ([F--H--F]):
• A doublet is appeared in 19F NMR spectrum
= (2nI + 1) n=1
= (2  1  1/2) + 1 (only one hydrogen)
=2

PR3 = pyramidal
For example, PF3:
• All fluorines are chemically equivalent and hence expected a singlet.

• However, the fluorines are attached P which is a NMR active nuclei (31P; I =
1/2). Hence a doublet is appeared in 19F NMR spectrum
Dr. D. Suresh 19F nuclei in absence of 31P = (2nI + 1)

sureshvnr@gmail.com19F nuclei coupled with 31P
= (2  1  1/2) + 1
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=2
Coupling to spin-1/2 isotopes of 100% abundance: BR4- = tetrahedral
In 11B NMR spectrum of [BH4]-:

• Expected a singlet in the 11B NMR.
• But due to the coupling of 1H with
11B, resulted in a quintet peak.
= (2nI + 1)
= (2  4  1/2) + 1
=5
BR4- = tetrahedral
In 11B NMR spectrum of [B(CF3)4]-:
= (2nI + 1)
= (2  12  1/2) + 1
= 13
• Expected a singlet in the 11B NMR.
Dr. D. Suresh
• But due to the coupling of 19F with
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11B, resulted in a 13 line peak. 336
31P NMR of PF6- PR6- = octahedtral
• Expected a singlet in the 31P NMR.

• But due to the coupling of 19F with
31P, resulted in a septet peak.
19F NMR of PF6-
• Expected a singlet in the 19F NMR.

• But due to the coupling of 31P with
Dr.resulted
D. Suresh
19F, in a doublet.
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31P NMR of P(OCH3)3 PR3 = pyramidal
• Expected a singlet in the 31P
NMR.
• But due to the coupling of 1H
with 31P, resulted in a 10 peak.
31P {1H} NMR of P(OCH3)3 PR3 = pyramidal
• Only a singlet in the 31P{1H} NMR.

• The coupling of 1H with 31P is
decoupled.
Dr. D. Suresh
• 31P NMR is always performed with proton
To simply by the spectrum, the
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decoupling which is indicated as 31P{1H}. 338
• To simply by the spectrum, the 31P NMR is always performed with proton
decoupling which is indicated as 31P{1H}.
31P NMR of
31P{1H} NMR of
Septet
Septet
P-O-CH2
P-CH2
2J
3J
PH = 2.6 Hz PH = 8.06 Hz
P-O-CH2 P-CH2
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31P {1H} NMR of fac-[Cl3Rh(PPh3)3]; Rh is NMR active nuclei with I = 1/2 (100 %)
• In case of facial isomer, all the P ligands are
equivalent. Hence, only one signal in 31P NMR.
• But due to 109Rh coupling they appear as
doublet.
31P NMR of mer-[Cl3Rh(PPh3)3]; Rh is NMR active nuclei with I = 1/2 (100 %)
• In case of meridonal isomer the P ligands are in two
different environment. (2P are trans to one another and
1P is trans to Cl). Hence, two signal in 31P NMR.
• Due to coupling (P-P), they appear as doublet
PA PB
with intensity 2 and triplet with intensity 1.
• This will further splitting with 109Rh, the doublet
Dr. D. Suresh P-P
will split into doublet of doublet.
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Rh-P
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• The is split into doublet of triplet.
31P{1H} NMR of PhMe2P:BH3 PR4 = tetrahedral
• Only a singlet in the 31P{1H} NMR is expected.
• The coupling of 1H with 31P is decoupled.
• But 11B couples with 31Pin 31P NMR spectrum to
= (2nI + 1)
give 4 lines B; I = 3/2 n = 1
= (2  1  3/2) + 1
(only one boron)
31P NMR of PF2H(15NH2)2 =4
• Expected a singlet in the 31P NMR.

• Coupled with 1H to give doublet.
• The doublet further coupled with 19F to give each a triplets.
• Doublet of triplets coupled with 15N to give another set of
Dr. D.
Total of 90
Suresh
triplets each
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lines • This will further couple with 1H to give each quintet
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31P NMR of PF2H(15NH2)2
3. Further coupling of
31P with 19F (t)
1. 31P nuclei in absence other nuclei

2. 31P nuclei
coupled with 1H (d)
4. Further coupling
of 31P with 15N (t) Total of 90 lines
5. Further coupling
of 31P with 1H (quin)
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1H NMR Spectrum
Coupling is not observed

between phosphorus
and the proton of the
hydroxyl group
19F NMR Spectrum 31P NMR Spectrum
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1H NMR Spectrum
31P NMR Spectrum

19F NMR Spectrum
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In 1H NMR spectrum:
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To find the number of lines for the given molecules….
are given by
Find the number of signals in 31P NMR of PF2H(15NH2)2:

• In this case for 31P NMR, there are three active nuclei 1H (two different), 19F,
and 15N; all are having I value of +1/2

Number of signals = (2nHIH + 1)  (2nH-NIH + 1)  (2nFIF + 1)  (2nNIN + 1)
in 31P NMR
= ([2(1)H1/2] + 1)  ([2(4)H-N1/2] + 1)  ([2(2)F1/2] + 1)  ([2(2)N(1/2)] + 1)
Dr. D. Suresh
= (1 + 1)  (4 + 1)  (2 + 1)  (2 + 1)
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 5  3 58876
= 288703  3 = 90 lines 346
• In this case for 1H NMR, there are one active nuclei 31P
(two types); having I value of +1/2
Number of signals = (2n I + 1)  (2n I + 1)

Pa Pa Pb Pb
in 1H NMR
= ([2(1)Pa1/2] + 1)  ([2(2)Pb1/2] + 1)
= (1 + 1)  (2 + 1)
= 2  3 = 6 lines
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• In this case for 1H NMR for Ha, there are two active
nuclei 1Hb and 31P (two types); all are having I value of
+1/2
Number of signals = (2nHbIHb + 1)  (2nPaIPa + 1)  (2nPbIPb + 1)
in 1Ha NMR = ([2(1)Hb1/2] + 1)  ([2(1)Pa1/2] + 1)  ([2(2)Pb1/2] + 1)
= (1 + 1)  (1 + 1)  (2 + 1)
= 2  2  3 = 12 lines
• 1H NMR for H , there are two active nuclei 1H and
b a
31P (two types); all are
having I value of +1/2
Number of signals = (2n I + 1)  (2n I + 1)  (2n I + 1)
Ha Ha Pa Pa Pb Pb
in 1Hb NMR
= ([2(1)Ha1/2] + 1)  ([2(1)Pa1/2] + 1)  ([2(2)Pb1/2] + 1)
Dr. D. Suresh
= (1 + 1)  (1 + 1)  (2 + 1)
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= 2 88703
2  3 = 58876
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12 lines
GATE 2011
1H 31P
For 1H NMR
Number of signals = (2nFIF + 1)  (2nPIP + 1)
= ([2(1)1/2] + 1)  ([2(2)1/2] + 1) P-H
H-F
= (1 + 1)  (2 + 1) = 2  3 = 6
For 31P NMR
Number of signals = (2nFIF + 1)  (2nHIH + 1) P-F
= ([2(1)1/2] + 1)  ([2(1)1/2] + 1) H-P
Dr. D. Suresh = (1 + 1)  (1 + 1) = 2  2 = 4
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CSIR, December 2017
2nI + 1
231/2 +1 = 4 P-H
2nI + 1
P-B
213/2 +1 = 4
quartet of quartet
For 31P NMR

Number of signals = (2nHIH + 1)  (2nBIB + 1)
= ([2(3)1/2] + 1)  ([2(1)3/2] + 1)
Dr. D. Suresh = (3 + 1)  (1 + 1) = 4  4 = 16 line
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Coupling to spin-1/2 isotopes of low abundance: Satellite peaks:
• Many NMR studies involve isotopes of low natural abundance, such as 13C,
15N, 29Si and 183W, known as dilute spins.

• Dr. abundant
Less D. SureshX nuclei show satellite peaks on the main peak.
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• The intensity of each satellite will be half of the abundance of that isotope.
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Coupling to spin-1/2 isotopes of low abundance:
Satellite peaks:
• Both 31P and 195Pt are NMR active nuclei.
• In 31P{1H} NMR it should appear as doublet.
• However 31P{1H} NMR shows a singlet and a doublet (satellite peaks)
• This due to low abundance (33.8%) of 195Pt, the doublet appeared as
satellite peaks.
31P NMR spectrum
satellite peaks
Intensity of each
satellite will be half
of the abundance of
Dr. D. Suresh that isotope
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Satellite peaks:
• Both 31P and 77Se are NMR active nuclei.
• In 31P{1H} NMR it should appear as doublet.
• However 31P{1H} NMR shows a singlet and a doublet (satellite peaks)
• This due to low abundance (7.58%) of 77Se, the doublet appeared as
satellite peaks.
31P NMR spectrum
satellite peaks
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Satellite peaks:
13C satellite peaks

For ortho, 2JP-13C
For meta, 3JP-13C
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Satellite peaks:
19F NMR spectrum of [XeF5]-
• Both 19F and 129Xe are NMR active nuclei.
• In 19F NMR it should appear as doublet.
• However 19F NMR shows a singlet and a doublet (satellite peaks)
• This due to low abundance (26.4%) of 129Xe, the doublet appeared as
satellite peaks.
satellite peaks
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Match 1H NMR spectrum with the complex (only the hydride region is given):
Pt satellite peaks
Pt satellite peaks
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Pt(less abundant) H (100%) and P (100%) are NMR active nuclei
பால்: அறத்துப்பால் அதிகாரம்: பபானறயுனைனை குறள்: 155
ஒறுத்தாவர ஒன்றாக வையாயர வைப்பர்
சபாறுத்தாவரப் சபான்யபாற் சபாதிந்து
• தமக்கு இவைக்கப்படும் தீவமவயப் சபாறுத்துக் சகாள்பைர்கவை
உலகத்தார் சபான்னாக மதித்துப் யபாற்றுைார்கள். சபாறுத்துக்
சகாள்ைாமல் தண்டிப்பைர்கவை அதற்கு ஒப்பாகக் கருத
மாட்டார்கள்.
Translation:
• Who wreak their wrath as worthless are despised;

• Who patiently forbear as gold are prized.
Explanation:
Dr. D. Suresh
• (The wise) will not at all esteem the resentful. They will esteem the patient
88703
just as the58876
gold which they lay up with care.
Dr. D. Suresh
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are given by
Dr. D. Suresh
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88703 58876
Fluxional behavior (Stereochemically non-rigid species):
• A fluxional molecule is one that
undergoes a dynamic molecular
process that interchanges two or
more chemically and/or
magnetically different groups of a
molecule.
• If the rate of this exchange is faster
than the time scale of
spectroscopic observation, these
two different groups can appear to
be identical.
Dr. D. Suresh • The process can also be called as
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dynamic exchange process.360
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• Changes in the 1H NMR spectrum of a two-site system on warming of the HA
and HB protons begin to exchange at rates comparable with the NMR
timescale
High temperature limit
decreasing
coalescence the
temperature
Initial broadening
Dr. D. Suresh
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Low temperature limit
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• Many metallocenes exhibit fluxionality and undergo internal rotation because
the barrier to the interconversion of the various forms is low.
Fluxionallity in (5-C5H5)(1-C5H5)Fe(CO)2:
• (5-C5H5)(1-C5H5)Fe(CO)2 has interesting NMR behavior.

This compound contains both 1 and 5 cp ligands.
• The 1H NMR spectrum at room temperature shows two singlets of equal

area at 4.5 and 5.7 ppm.
• A singlet would be expected for the five equivalent protons of the 5-C5H5
ring but is surprising for the 1-C5H5 ring, because the protons are not all
equivalent.
• At lower temperatures, the peak at 4.5 ppm (5-C5H5) remains constant, but
Dr. D. Suresh
the other peak at 5.7 ppm spreads and then splits into new peaks near 3.5
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and between 5.9 and 6.4 ppm, consistent with a 1-C5H5 ligand
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1 2 3 4 5 1
1H-NMR
Ring Whizzer
Mechanism 5.7 ppm 4.5 ppm five ring positions
of the mono-
hapto
ring interchange
via 1,5-hydride
shifts
Dr. D. Suresh 4.5 ppm

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At 62 C a single line is observed,
1H-NMR
indicating dynamic process that
renders the four ligands
equivalent
At -27 C interconvention of
mono- and pentahapto ligands is
occurring slowly enough that both
configurations are observable in
the spectrum.
Even at -27 C, the monohapto

rings are involved in a dynamic
process that averages the signals
for the three types of ring
protons.
Only at -80 C this process also is

slowed so that the peak for the
Dr. D. Suresh monohapto ligands reemerging in
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364
88703 58876 non-equivalent ring protons at.
1H NMR at 25 C 1H NMR at – 85 C
Solvent peak Solvent peak

2H
1H 4H 2H
1H
quintet and doublet

Dr. D. Suresh
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• Five-coordinate species such as PF5 and BrF5 constitute one group of
compounds for which the activation barrier for dynamic behavior in solution
is relatively low, and exchange of substituent positions is fast.
• The room temperature solution 19F NMR spectrum of

BrF5 exhibits a doublet and a quintet (due to 19F–19F
coupling) with relative integrals of 4:1.

• Above 450 K (177 C), one signal is observed,
indicating that the five F atoms are equivalent on the
NMR timescale, i.e. the BrF5 molecule is fluxional
• Conversely, the room temperature solution 19F NMR

spectrum of PF5 exhibits singlet only.
Dr. D. Suresh
• Only at lower temperature, the compound show triplet and
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quartet.
• [Fe(CO)5] shows just one 13C resonance at room
temperature, indicating that all five CO groups are
equivalent.
IR
• However, the IR spectrum shows distinct axial and
equatorial CO groups, and by implication a trigonal-
bipyramidal structure.
• The observed 13C-NMR spectrum of [Fe(CO)5] is at
+ 30 C due to the fast exchange of CO and 13C-NMR
weighted average of these separate resonances.

• The temperature of sample while recording NMR
can easily be changed. Hence samples can often
be cooled down to a lower temperature ( 60 C)
Dr. D. Suresh
and the rate of interconversion becomes slow
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enough get separate resonance signals.
• The mechanism by which the axial and equatorial atoms can exchange with
one another so rapidly is explained by Berry pseudorotation (BPR).
• Ligand–ligand repulsions
are minimized in a
trigonal bipyramidal
arrangement, only a
small amount of energy
is needed to convert it
into a square-based
pyramid.
• The interconversion involves small perturbations of the bond angles

subtended at the central atom, and continued repetition of the process
Dr. D. Suresh
results in each substituent ‘visiting’ both equatorial and axial sites in the
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trigonal bipyramidal structure
31P{1H}-NMR
At room temperature the scrambling
of the PMe3 groups makes them all
equivalent and a doublet is
observed (from coupling to 103Rh).
H
H H
C
(Me)3
P
Rh P(Me)3
(Me)3P
P(Me)3
(CH3)Rh(PMe3)4
At 80 C the spectrum consists of a doublet of doublets of
relative intensity 3, which arises from the equatorial P
Dr. D. Suresh atoms (coupled to 103Rh and the single axial 31P), and a
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103Rh and the three equatorial 31P 369
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CSIR December 2015
• Whenever there is a axial and equatorial positions are there with same
ligands, the molecule tend to show fluxional behavior.
• Dr. D. Suresh
Whenever there is lower x–ligands (x is not the maximum hapticity) are
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there then the molecule tend to show fluxional behavior
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CSIR June 2016
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CSIR June 2016
• Fluxional molecules that undergo dynamics

such that some or all of their atoms
interchange between symmetry equivalent
positions.
• In Fe(CO)5 is the archetypal fluxional
molecule due to rapid interchange of the
axial and equatorial CO group
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CSIR December 2015
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CSIR June 2012
CSIR June 2014
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NMR spectrum for Paramagnetic molecules:
• The two most obvious characteristics of NMR spectra of paramagnetic
materials are the broadening of the resonance peaks and a great expansion
of the normal chemical shift scale.
• The signals from diamagnetic materials could also show these effects in the
presence of paramagnetic species, even in low concentrations.
• For example, Ru2Cl4(-CO)(PPh3)4
31P{1H} spectrum
One of Ru is in +3
Dr. D. Suresh Ru(II)

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• The line broadening in spectra of paramagnetic compounds is caused by
short electronic spin-lattice relaxation times and/or hyperfine electron-
nuclear coupling.
• Consequently, it is usually the case that materials giving useful EPR spectra
have nuclear magnetic resonances so broad as to be unobservable.
Isotropic shiftc or contanct NMR shift:
• The difference between the chemical shift of a given nucleus in a

diamagnetic and paramagnetic environments is called the isotropic shift.
• Isotropic shifts result from two mechanisms, contact shifts (scalar shifts) and
pseudocontact shifts (dipolar shifts).
Dr. D. Suresh
• Both effects operate simultaneously but one or the other term can be
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dominant.
Isotropic shift or Paramagnetic shit:
• The isotropic chemical shift for Cp ring in nickelocene is -255.8 ppm, which
is the difference between the observed shift (ca. -260 ppm) and the shift
observed for a diamagnetic analogue ferrocene (ca. 4.2 ppm).
paramagnetic
compound
-260 ppm
202 ppm
4.2 ppm
diamagnetic
compound
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Contact shift or Scalar shift:
• Contact shifts result from spin polarization conveyed through the molecular
orbitals of the molecule.
• The origin of contact shift can be understood if we consider coupling
between the electron and the nucleus, which would give a doublet in the
NMR spectrum under conditions of slow electronic spin-lattice relaxation, but
with a large (millions of Hz) coupling constant..
• With such a large coupling, the intensities of the two resonances are not
equal, so their weighted mean position is not midway between them.
• Under fast relaxation conditions the doublet collapses back to a singlet at
the weighted mean position, and so may fall some thousands of Hz away
from the expected position – the contact shift.
• Contact shifts give a measure of unpaired spin density at the resonating
Dr. D. Suresh
nucleus, and so are particularly useful in studying the spin distribution in
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radical species, or in ligands in organometallic compound.
Pseudo-contact shift or Dipolar shift:
• There is a through-space dipolar interaction between the magnetic moments
of the electron and the resonating nucleus, which gives a dipolar shift, also
sometimes known as a pseudo-contact shift.
• The chemical shift is caused by the dipolar coupling between the magnetic
moments of the nucleus and of the unpaired electron.
• This situation is somewhat similar to the case of j-coupling where we would
expect the NMR peak to split into a doublet due to the coupling with the
magnetic moment of the unpaired electron.

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Lanthanide shift reagents:
• The 1H NMR spectra of large organic compounds or of mixtures of
diastereoisomers, for example, are often difficult to interpret and assign due
to overlapping of signals.
• This is particularly true when the spectrum is recorded on a low field (e.g.
100 or 250 MHz) instrument.
• The low- and mid field NMR instruments remain in daily use for research,
and in these cases, paramagnetic NMR shift reagents may be used to
disperse overlapping signals.
• Lanthanide metal complexes containing –diketonate ligands are routinely
employed as NMR shift reagents. Hence it is referred as Lanthanide shift
reagents.
• Dr.example,
For D. Suresh
the 1H NMR of 1-hexanol is very complicated due to the
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splitting pattern of nearly the same hydrogen atom.
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1HNMR spectrum of n-hexanol
without the present of shift
reagents
1H NMR spectrum of n-hexanol in the

present of 6.5% shift reagents
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• The addition of a small amount of a shift reagent (lanthanide metal
containing complexes) to a solution of an organic compound can lead to an
equilibrium being established between the free and coordinated organic
species.
• The induces shifts are due to pseudo-contact or dipolar interactions between
the shift reagents and the sample.
• The result is that signals due to the organic species which originally
overlapped, spread out, and the spectrum becomes easier to interpret.
• The amount of shift reagents can be added till a sufficient resolution is
obtained.
• NMR shift reagents are mostly contains the lanthanide metals (Eu, Yb, Pr)
with fluorinated -diketonate as ligands.
Dr. D. Suresh
• Eu and Yb derived shift reagent causes downfield shift while Pr derivative
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one upfield shift in NMR spectra
Lanthanide shift reagents: Chiral shift reagents
EuFOD
Applications of Lanthanide shift reagents:

1. To simplify the complicated spectra
• separation of overlapping signals
• easier assignment
• integration of signals which are otherwise overlapped
Dr. •D. Suresh experiments
decoupling
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Applications of Lanthanide shift reagents:
2. To differentiate the olefinic and aromatic protons
• When silver containing shift reagents are added for example Ag(FOD), they
make complexes with -electrons and the shifts are observed for olefins and
arenes.
3. To differentiate the enantiomers
• Enantiomers are not distinguishable by NMR and not possible to determine
if the sample is a pure enantiomer or a racemic mixtures.
• But with the help of a chiral shift reagent it possible to differentiate by

Dr. D. Suresh
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forming diastereoisomers or diastereomeric complexes.
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Applications of Lanthanide shift reagents: Chiral shift reagents
Differentiating the enantiomers
Enantiomeric excess
R:S, 20:80
With
Chiral shift reagents
Racemic mixture
R:S, 1:1
With
Dr.
WithD.outSuresh
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பால்: அறத்துப்பால் அதிகாரம்: பயனில பசால்லானை குறள்: 197
நயனில சசால்லினுஞ் சசால்லுக சான்யறார்
பயனில சசால்லாவம நன்று
• பண்பாைர்கள், இனிவமயல்லாத சசாற்கவைக்கூடச் சசால்லி
விடலாம்; ஆனால் பயனில்லாத சசாற்கவைச் சசால்லாமல்
இருப்பயத நல்லது.
Translation:
• Let those who list speak things that no delight afford,

• 'Tis good for men of worth to speak no idle word.
Explanation:
Dr. D. Suresh
• Let the wise if they will, speak things without excellence; it will be well for
88703
them 58876
not to speak useless things.
Dr. D. Suresh
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388
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ESR or EPR Spectroscopy
• Electron Spin Resonance (ESR) or Electron
Paramagnetic Resonance (EPR) spectroscopy
is invented by Zavoiskii in 1944, is similar to
NMR spectroscopy.
• ESR spectroscopy is an absorption
spectroscopy which involves the absorption of
radiation in the microwave region (104 - 106
MHz) by substances containing one or more
unpaired electrons.
• This absorption of microwave radiation takes
place under the influence of an applied
magnetic field.
• Dr. substances
The D. Suresh with one or more unpaired
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electrons are paramagnetic and exhibit ESR.
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Theory of Electron Spin Resonance
• When a charged particle such as a electron spins on its
axis, it creates a magnetic field. Thus, the electron can be
considered to be a tiny bar magnet.
• Generally, these tiny bar magnets are randomly

oriented in space.
• However, in the presence of an external

magnetic field H0, they can oriented with or
against the applied field. (Zeeman Effect)
• More electron are oriented with the applied

field because this arrangement is lower in
Dr. D.
energy.Suresh
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• The energy difference between these two states is very small (<0.1 cal)
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• charged particle spins on its axis and creates a
magnetic field and acts like a tiny bar magnet
E nucleus aligned
against H0 Ms = =+ 1/2
nucleus aligned Ms = -1/2

with H0
Ms = electron spin
External magnet quantum number
with field H0
• Now two energy states for a electron: a lower energy state with the electron
Dr. D. Suresh
aligned in the same direction as H0, and a higher energy state in which the
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58876against H0.
391
electron
• When an external energy source (h) that matches the energy difference
(E) between these two states is applied, energy is absorbed, causing the
electron to “spin flip” from one orientation to another.
Absorbing microwave radiation
causes the electron to spin flip
H0
• The energy difference between these two electron spin states corresponds
to microwave region of the electromagnetic spectrum.
Dr. D. Suresh
• An electron is in RESONANCE when it absorbs microwave radiation and
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spin flips to a higher energy state
ms = + 1/2
E = h = gNH0
Spinning
electron
ms = - 1/2
g – spectroscopic splitting factor; N– Bohr magneton

H0 – External magnetic field; Ms- Spin quantum number
g – spectroscopic splitting factor also called as Lande splitting factor
• The frequency need for resonance and the applied magnetic field strength
are directly proportional to each other.
• Larger the applied external magnetic field (H0), greater the energy difference
Dr. D. Suresh
(E) between the two states, higher the microwave frequency () needed for
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resonance 393
ms = + 1/2
E = h = gNH0
ms = - 1/2
• Because of instrumental considerations associated with the signal-to-noise

Dr. D. Suresh
ratio, ESR spectra are generally recorded as first derivative spectra.
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Typical ESR Spectra
normal spectrum normal spectrum
Dr. D. Suresh
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first derivative spectrum first derivative spectrum
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Selection Rule:
• In ESR, the selection rule refers to the spin quantum number m; only
transitions in which m changes by one (up or down) are allowed.
• This is sometimes expressed as
ms = ms(initial state) - ms(final state) = ± 1.
• Another way of saying this is that one spin can flip between 'up' and 'down'
or vice versa.
• In the case of spin a single spin-half, the change in m between the two
states is [(+1/2) - (-1/2)] = 1, so the transition is allowed.
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Lande Splitting factor or g-factor, the chemical shift
E = h = gNH0
• Lande splitting factor or “g” factor is not constant but it depends on the
environment of the unpaired electron.
• The value of g depends on the orientation of the molecule containing the
unpaired electron with respect to the applied magnetic field.
• It also depends on the physical state of the sample.
• In gas and liquid states, the molecules have free motion and the value of g is
averaged over all orientations.
• In case of a paramagnetic ion or radical situated in a perfectly cubic crystal
site, the value of g does not depend on the orientation of the crystal, i.e. it is
the same in all directions.
• Dr. D. Suresh
However, in case of a paramagnetic ion or radical with low symmetry, the
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value of g depends on the orientation of the crystal.
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h
g=
NH0
• In measuring the g values of free radicals, it is convenient to measure the

field separation between the center of the spectrum of the unknown sample
and that of a reference substance whose g value is accurately known.
• The most widely used reference is 1,1-diphenyl-2-picrylhydrazyl free radical
(DPPH) which is completely in free radical state and its g value is 2.0036.
• The reference substance is placed along with

the unknown in the same dual resonant
cavity.
• Dr. signals
Two D. Suresh
will be observed simultaneously
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with a field separation of H0. DPPH
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The g factor for unknown sample is given by
ΔHo gref = g factor of reference
gunknown = gref(1 − )  = the resonance frequency

• H0 is positive if the unknown has its center at a higher field than the
reference
• The peak value is measured from the center of the signal
• For a free electron g = 2.00232
• For organic radicals g = 1.99 - 2.01
• For transition metal compounds g = 1.4 –

3.0 (Large variations due to spin-orbit
Dr. D. Suresh
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The Lande splitting factor can be theoretically obtained by,
We will study
in detail in III 3 S(S + 1) − L(L + 1)
gj = +
Semester 2 2J (J + 1)
The values S and J can be taken from the “Term Symbol”
For example,
Dr. D. Suresh
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Splitting in ESR Spectroscopy
There are two types of splitting structures in ESR spectroscopy,
(i) hyperfine splitting
(ii) fine splitting
Hyperfine splitting:
• Hyperfine structure results from coupling of the unpaired electronic spin with
neighboring nuclear spins. (similar to spin-spin coupling).
• If the nucleus is having unpaired electron, then the spectral line will split
further it is termed as super hyperfine splitting.
a = hyperfine coupling constant
Can be used to provide information
• Number and identity of nuclei
• Distance from unpaired electron
Dr. D. Suresh
“a” is measured as the distance
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between the centers of two signals
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Hyperfine Splitting
• Coupling patterns are same as that in NMR
• When only one nuclei is interacting, then the number of splitting lines are
given by
2nI + 1 n = number of equivalent nuclei
I = nuclear spin
are given by
• The splitted line intensities follow binomial distribution (Pascal’s triangle as
Dr. D.to Suresh
similar NMR)
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Interaction of electron spin with nuclei in ESR Spectroscopy
Which nuclei will interact?
• Isotopes with even atomic number and even mass number have I = 0, and
have no hyperfine splitting in EPR spectra
12C, 28Si, 56Fe, …(I = 0; no hyperfine splitting)
• Isotopes with odd atomic number and even mass number have I = 1,2,3..
have interaction and show hyperfine splitting in EPR spectra
2H, 10B, 14N, … (I = 1,2,3... Show hyperfine splitting)
• Isotopes with odd atomic number and odd mass number have I = 1/2, 3/2,...
have interaction and show EPR spectra show hyperfine splitting in EPR
spectra
1H, 13C, 19F, 55Mn, … (I = 1/2,3/2... Show hyperfine splitting)
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Common transition metal with their nuclear spins
Common ligands with their nuclear spins
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Splitting Pattern in ESR
Splitting Pattern in ESR with I= 1//2 2nI + 1
n=1 n=2 n=3
n=4 n=5 n=6
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Splitting Pattern in ESR
Splitting Pattern in ESR with I= 1 2nI + 1
n=1 n=2 n=3
n=4 n=5 n=6
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Hyperfine Splitting
ms = ± 1
Electron in
absence of
applied
magnetic field
2 lines
Electron in
presence of
applied Electron coupling
magnetic field to one
Dr. D. Suresh nucleus with
I = 1/2
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Hyperfine Splitting
The spin of H = 1/2, i.e. I = 1/2; The spin of H = 1/2, i.e. I = 1/2;
nH = 2 and 1 nH = 2 and 1
(two chemically non-equivalent proton) (two chemically non-equivalent proton)
no. of splitting line no. of splitting line

= (2nHaIHa + 1) (2nHbIHb + 1) = (2nHaIHa + 1) (2nHbIHb + 1)
Dr. D. Suresh
= (2(1)Ha(1/2)Ha + 1) (2(2)Hb (1/2)Hb + 1) = (2(1)Ha(1/2)Ha + 1) (22Hb (1/2)Hb + 1)
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= (1 + 1) (2 + 1) = 6 lines = (1 + 1) (2 + 1) = 6 lines 409
Predicting ESR spectrum
[13CH3]
.
The spin of 13C = 1/2, i.e. I;= 1/2; nC = 1;
The spin of H = 1/2, i.e. I = 1/2; nH = 3
no. of splitting line = (2naIa + 1) (2nbIb + 1)

= [(2  1  1/2) + 1] [(2  3  1/2) + 1]
= 8 lines
[13CF2H]
.
The spin of 13C = 1/2, i.e. I;= 1/2; nC = 1;
The spin of F = 1/2, i.e. I;= 1/2; nF = 2
no. of splitting line = (2naIa + 1) (2nbIb + 1) (2ncIc + 1)
= [(2  1  1/2) + 1] [(2  1  1/2) + 1] [(2  2  1/2) + 1]

Dr. D. Suresh
= (2) (2) (3)
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= 12 lines
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ESR spectrum of 1,4-benzosemiquinone
all the four protons are equivalent and the unpaired electron is
coupled with four equivalent protons
2nI + 1
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Predicting ESR spectrum
The spin of 14N = 1, i.e. I;= 1; nN = 2;
no. of splitting line = (2naIa + 1)

= [(2  2  1) + 1]
= (4 + 1)
= 5 lines
[PH4]  [PH3]
.
The spin of P = 1/2, i.e. I;= 1/2; nP = 1;


= [(2  1  1/2) + 1] [(2  3  1/2) + 1]
Dr. D. Suresh =24
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. Predicting ESR spectrum
[BH ]- .
[BH3 ]- radicals, generated by
3
BH4- + •C(CH3)3 [BH3•]- + HC(CH3)3 hydrogen abstraction from [BH4]-
ions using tert-butoxyl radicals
The spin of 11B = 3/2, i.e. I;= 3/2; nB = 1;

= [(2  1  3/2) + 1] [(2  3  1/2) +1]
= (3 + 1)  (3 + 1) = 4  4
= 16 lines
• The boron also have an I value of 3 for 10B
but that abundance is very low and

interaction is very weak.
Dr. D. Suresh
• Appeared as very small signals in the EPR
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spectrum
பால்: பபாருட்பால் அதிகாரம்: தீ நட்பு குறள்: 811
பருகுைார் யபாலினும் பண்பிலார் யகண்வம
சபருகலிற் குன்றல் இனிது.
• நல்ல பண்பு இல்லாதைர்கள் அன்பு சைள்ைத்தில் நம்வம
மூழ்கடிப்பதுயபால் யதான்றினாலும் அைர்கைது நட்வப, யமலும்
ைைர்த்துக் சகாள்ைாமல் குவறத்துக் சகாள்ையத நல்லது.
Translation:
• Though evil men should all-absorbing friendship show,
• Their love had better die away than grow.
Explanation:
• The decrease of friendship with those who look as if they would eat you up
Dr. D. Suresh
(through excess of love) while they are really destitute of goodness is far
88703
better than58876
its increase.
h
g=
NH0
(2naIa + 1) (2nbIb + 1)...
Dr. D. Suresh
sureshvnr@gmail.com
88703 58876
. Predicting ESR spectrum
[(MeO)3PBH2 ]
The spin of 11B = 3/2, i.e. I;= 3/2; nB = 1;
e
The spin of P = 1/2, i.e. I = 1/2; nH = 1
no. of splitting line = (2naIa + 1) (2nbIb + 1) (2ncIc + 1) e-P
= [(2  1  3/2) + 1] [(2  2  1/2) +1] [(2  1  1/2) +1]
e-H
= (3 + 1)  (2 + 1)  (1 + 1)
=432
e-B
= 24 lines (21 major lines + 3 weaker lines)
• The boron also have an I value of 3 for 10B
but that abundance is very low and

interaction is very weak.
Dr. D. Suresh
• Appeared as very small signals in the EPR
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spectrum
Splitting in ESR Spectroscopy
There are two types of splitting structures in ESR spectroscopy,
(i) hyperfine splitting
(ii) fine splitting
Fine splitting or fine structure:

• Fine structure results from coupling of the electron and electron spin
(Occurs when more than one unpaired electronic spins are present).
• Usually measured at low temperatures, or by diluting the sample.
• In general, if there are “n” parallel electron spins, there will be “n” equally
spaced resonance lines in the ESR spectrum.
• Many transition metal complexes contains more than one unpaired
Dr. D. Suresh
electrons.
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Electron Spin Resonance
Fine splitting or fine structure:
Electron Quadrupole or Zero-field splitting:
• Till now, we considered radicals with only one unpaired electron.
• However, there are many systems that have several unpaired electrons, and
these can also be studied by EPR
• The splitting of spin levels even in the absence of magnetic field is called
zero–field splitting.
• Occurs mainly in in transition metal complexes where there are more than
one unpaired electrons.
• Removes the degeneracy of transitions and more transitions are observed
Dr.expected,
than D. Sureshin the presence of external magnetic field.
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• Fine structure in ESR spectrum is obtained
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• A system with n unpaired electrons has a total spin equal to S = n/2.
• Such a system has a spin multiplicity of 2S + 1 and this value is equal to the
number of spin energy levels.
• An essential difference between S = 1/2 (only one unpaired electron)
systems and high-spin or S ≥ 1 (more than one unpaired electrons) systems
is that the latter are subject to an extra magnetic interaction namely between
the individual unpaired electrons.
• Since each spin produces a small magnetic field in the vicinity of its
partner.This interaction is always present and is independent of any applied
external magnetic field.
• This interaction is therefore referred as zero-field interaction.
•
Dr. D. Suresh
An important theorem that summarizes the properties of multielectron
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systems is Kramers' rule
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Kramer’s degeneracy or Kramer’s rule:
• When the species contains an odd number of unpaired electrons, the spin
degeneracy of every level remains doubly degenerate S = n/2. (3/2, 5/2,
etc.).
• When the number of unpaired electrons is even, crystal field may remove
the spin degeneracy entirely. S = n. (1, 2, etc.)
• This is known as Kramer’s degeneracy. “any ion with an odd number of electrons
must always have as its lowest level at least
Magnetic field a doublet”, called a Kramers' doublet.
if only one
unpaired electron Odd number
Splitting Kramer’s degeneracy applies and
is present
of energy each level must remain
doubly degenerate
Crystal field
if more than one Even number
Dr. D. Suresh
unpaired electron
is present
Crystal field removes the spin
degeneracy completely
sureshvnr@gmail.com i.e. non-degenerate 420
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Kramer’s degeneracy or Kramer’s rule:     
        
2-unpaired 3-unpaired electron 4-unpaired 5-unpaired electron

electron (odd number) electron (odd number)
(even number) Doubly degenerate (even number) Doubly degenerate
non-degenerate (two Kramer’s doublet) non-degenerate (three Kramer’s doublet)
Dr. D. Suresh
“any ion with an odd number of electrons must always have as its
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lowest level at least a doublet”, called a Kramers' doublet
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+1  
With Zero-field splitting
When 2 unpaired electron    
   
ms = ± 1
   
When 3 unpaired electron +3/2   

     
ms = ± 1
  
  
  
Dr. D. Suresh   
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88703 58876      
422
even number –
spin degeneracy entirely
odd number
all are doubly degenerate
Dr. D. Suresh
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Kramer’s degeneracy /Rule:
For example, d5, Mn2+ high spin system
Odd number of unpaired electrons and
     hence all are doubly degenerate
S = 5/2 and hence Ms =  5/2,  3/2,  1/2 ms = ± 1
+ 5/2     
+ 3/2     
+ 1/2
 5/2     
      3/2
No filed  1/2 - 1/2     
Zero filed
- 3/2
    
- 5/2     
Magnetic filed
•
Dr. D. Suresh
Five predominant peak will be appear due to fine splitting.
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• Further, due Mn (I = 5/2), each line will split into six (2(1)(5/2)+1) lines424
88703 58876
Kramer’s degeneracy /Rule:
e
For example, d5, Mn2+ high spin system
e–e
e – Mn
30 lines
• Five predominant
peak will be
appear due to fine
splitting.
1 3 Mn2+
2
4 5
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• Further, due to Mn (I = 5/2), each line will split into six (2(1)(5/2)+1) lines
For example, d8, Ni2+ system
    
Even number of unpaired electrons and
hence all are spin degeneracy
S = 1 and hence Ms =  1, 0,
+1
    
1
     0
0     
No filed Zero filed
-1
Dr. D. Suresh     
sureshvnr@gmail.com Magnetic filed
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CSIR June 2013
doublet
doublet
GATE 2011
HCU, 2015
Dr. D. Suresh
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EPR for Transition-metal complexes:
• EPR spectra of transition-metal complexes is complicated by the fact that
they usually have several approximately degenerate orbitals, and several
unpaired electrons.
• In a free transition-metal ion, the five d orbitals are degenerate, but in a
complex the orbitals do not interact equally with the ligands, and so the
levels are split into two or more groups (t2g and eg).
• For an octahedral complex there are three degenerate lower levels and an
upper pair, but there are other arrangements of orbital energies for other
types of complex.
• In analyzing any one system, we must ascertain the number of d electrons,
and whether the complex is high-spin or low-spin.
• The consequences of Jahn–Teller distortion, which removes the degeneracy
Dr. D. Suresh
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of any orbitally degenerate ground state, and of zero-field splitting and
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Kramer’s degeneracy, must also be considered.
Transition-metal complexes with one unpaired electron:
After this, if the metal center is

NMR active nuclei, this will
Dr. D. Suresh further split into several
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Transition-metal complexes with more than one unpaired electron:
(with out Jahn Teller distortion)
Jahn Teller
distortion
Dr. D. Suresh
sureshvnr@gmail.com here no
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Jahn Teller distortion
Transition-metal complexes with more than one unpaired electron:
(with Jahn Teller distortion)
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• EPR spectra of transition-metal species can be very difficult to interpret.

• But they are very important.
• Hence to simply, the study on the hyperfine splitting patterns and, the
electron distribution will be sufficient.
Predicting ESR spectrum of Inorganic complexes

• First step is to find the oxidation state of the transition metal.
• Then the number of d-electrons and the number of unpaired electrons.
• Then by using the formula,
no. of splitting line = (2naIa + 1) (2nbIb + 1)…

Dr. D. Suresh
sureshvnr@gmail.com n is the number of unpaired electron
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bis-salicylaldimine copper(II)
• First find the oxidation state of Cu, and it is found to
be Cu2+ so the number of d-electron is 9.
• There is only one unpaired of electron.
    
For copper, I = 3/2
So, (2nI + 1) The four line can be

= ([2  (1)  3/2] + 1) further split into several
= (3 + 1) = 4 lines lines due to N and C-H.
For Nitrogen I = 1 and hydrogen I = 1/2

DPPH
So, (2nNIN + 1) (2nHIH + 1) (standard)
Each four line will be
= ([2  (2)  1] + 1) ([2  (2)  1/2] + 1)
Dr. D. Suresh further split into 15 lines
= (4 + 1) (2 + 1) = 5  3 = 15 lines
sureshvnr@gmail.com due to 2N and 2 H.
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bis-salicylaldimine copper(II)
• When the N-H groups are replaced with N-D, the

EPR gave an identical spectrum.
• When the C-H groups are replaced with C-CH3, the EPR spectrum is
completely different.
• The EPR shows four main groups of line due to splitting with Cu (I = 3/2) and
each four lines are further split into fifteen lines due to coupling with two
nitrogen (I = 1).
• The hyperfine splitting by the N-H proton and that by the protons on the
methyl group are too small to be detected.
Dr. D. Suresh
This furnishes conclusive proof of the delocalization of the odd electron
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434
in this complex onto the ligand.

• Oxidation state of W is 0 and the number of d-
electron is 6 and all are paired.
• Hence there is no fine splitting.
• Nitrogen with 100% abundance having I value of
1.
• Two different nitrogen (coordinated and non-
coordinated)
• It couples with the radical electron to give
hyperfine splitting.
• This indicates that the electron is coupling to two
pairs of two 14N nuclei, which is consistent with
the lower symmetry in the proposed structure,
• So, again with the electron on the central ring.
Dr. D. Suresh
(2nI + 1) (2nI + 1) = ([2  (2)  1] + 1)  ([2  (2)  1] + 1)
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= (458876
435
+ 1)  (4 + 1) = 5  5 = 25 lines
[VO(acac)2]
• First step is to find the number of d-electrons.
• Here it’s a d1 (vanadium is in +4 oxidation state) system.
• Only one unpaired electron is there.
The spin of V = 7/2, i.e. I;= 7/2; nV = 1;
no. of splitting line = 2naIa + 1
After this, if the metal = [(2  1  7/2) + 1]

center is NMR active
nuclei, this will further = 7+ 1
split into several energy
levels
= 8 lines
Dr. D. Suresh
sureshvnr@gmail.com
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436
Co3(CO)9Se • The EPR shows a 22 line spectrum.
• Confirming only one unpaired electron and the
Cobalt’s are in 2/3 oxidation state.
= Co = Se
• If there is one unpaired electron in Cu2+ (I = 3/2) and the copper ion is
coordinated by one nitrogen atom (I = 1) and one OH- (I = 1/2), how many
lines can be expected in the EPR spectrum?
=(2nCuICu + 1)  (2nNIN + 1)  (2nHIH + 1)

=([2  1  3/2] + 1)  ([2  1  1] +1)  ([2  1  1/2] + 1)
Dr. D.= Suresh
(3 + 1)  (2 + 1) (1 + 1)
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= 4  3  2 = 24 lines
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437
பால்: அறத்துப்பால் அதிகாரம்: இன்ைாபசய்யானை குறள்: 320
யநாசயல்லாம் யநாய்சசய்தார் யமலைாம் யநாய்சசய்யார்
யநாயின்வம யைண்டு பைர்.
• சசய்யும் தீவம எல்லாம் சசய்தைர்க்யக, அதனால் நமக்குத் தீவம
யைண்டாம் என்பைர், அடுத்தைர்க்குத் தீவம சசய்யமாட்டார்.
Translation:
• O'er every evil-doer evil broodeth still;
• He evil shuns who freedom seeks from ill.
Explanation:
• Dr. D.will
Sorrow Suresh
come upon those who cause pain to others; therfore those, who
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desire to be free from sorrow, give no pain to others. 438
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Dr. D. Suresh
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Dr. D. Suresh
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Mössbauer Spectroscopy
• Mössbauer spectroscopy is otherwise referred as nuclear gamma resonance
spectroscopy.
• Mössbauer spectroscopy is based
on the resonant absorption of -

Recoil Free
radiation by nuclei and exploits the
fact that nuclear energies are
sensitive to the electronic and Recoil Free: implies that the emitted photon has
the exact frequency that corresponds to the
transition energy between the nuclear ground
magnetic environment.
state and the excited state.
• The Mössbauer effect makes use of
recoil-less or recoil-free absorption

Dr. emission
and D. Sureshof -radiation by a
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nucleus.
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Mössbauer Effect
• Rudolf Mössbauer discovered the Mössbauer Effect in 1957, while he was
working on his doctoral thesis, and received the Nobel Prize for Physics just
four years later.
• The basis of the effect is nuclear resonance between two nuclei of the same
isotope.
Processes involved in Mössbauer Effect
• One is in an excited
nuclear state and
relaxes by emission of
a  photon, while the

other absorbs this
photon and is thereby
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promoted into an
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excited state. 442
Dr. D. Suresh
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443
Periodic table of Mössbauer-active elements:
Dr. D. Suresh
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444
Nuclear parameters for selected Mössbauer isotopes:
Dr. D. Suresh EC = electron capture

sureshvnr@gmail.com  = beta decay
IT = isometric transition 445
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57Fe Mössbauer Spectroscopy
Principle:
• Consider a radioactive 57Fe**

26
57Co nucleus that
27
decays by electron
capture to produce an
57
excited state of 57 26 Fe*
26 Fe,
denoted by 2757Fe**.
• This nuclide decays to another excited state, denoted 57Fe*, that lies 14.41
eV above the ground state and which emits a -ray of energy 14.41 eV as it
decays.
• If a sample containing 57Fe (which occurs with 2 per cent natural
Dr. D. Suresh
abundance) is placed close to the source, the monochromatic -ray emitted
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by88703 58876
57Fe* can be expected to be absorbed resonantly. 446
Principle:
• However, because changes in the exact electronic and magnetic
environment affect the nuclear energy levels to a small degree, resonant
absorption occurs only if the environment of the sample 57Fe is chemically
identical to that of the emitting 57Fe* nucleus.
• Nuclei of any one element which are in different chemical environments will
have slightly different energy levels, but the environment-induced changes
are so small that it is possible to compensate for them with a Doppler shift of
the -radiation, achieved by moving the emitting nucleus either towards or
away from the absorber.

• The effect has been observed for relatively few nuclei at the concentrations
atDr. D. Suresh
which they occur in most coordination compounds, of which 57Fe and
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119Sn have been the most widely studied.
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Principle:
Typical Mössbauer Spectrum:
The Doppler effect (or the Doppler

shift) is the change in frequency or
wavelength of a wave (or other
periodic event) for an observer
Dr. D. Suresh moving relative to its source.
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448
• The selection rule for Mössbauer spectroscopy is ΔmI = 0, 1.
• The difference in absorption velocity and that of a suitable reference
standard is called the isomer (or chemical) shift; it is denoted  and is usually
expressed in units of mm s-1 or em s-1.
• The isomeric shift is directly affected by s-electrons while the p and d
electrons can just influence isomeric shift.
• As a result, different oxidation states, such as Fe(II), Fe(III), and Fe(IV), can
Dr. D. Suresh
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be distinguished as well as ionic and covalent bonding.
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Quadrupole splitting:
• A nucleus possesses a nuclear quadrupole moment if it has a spin I greater
than 1/2 i.e 3/2, 5/2.
• In this case, its energy levels will be affected by an electric field gradient
(EFG) at the nucleus, which leads to splitting of the Mössbauer line.
• For 57Fe the I value of ΔmI = 0, 1.
ground state is 1/2 which

do no show any IE = 3/2
quadrupole splitting but
excited state have I value
of 3/2 and hence show
quadrupole splitting Ig = 1/2
Dr. D. Suresh
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Only one line Two lines 450
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I > 1/2 nuclear quadrupole effect is observed
Quadrupole splitting:
• For a nucleus (129I) with I value of

ground state is 7/2 and excited
state is 5/2 show quadrupole
splitting in both the levels.
• Consequently the ground state

splits into four, and the excited state 8 lines for 129I
into three sub-states.
• This gives rise to a total of eight

possible transitions
Dr. D. Suresh
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451
Magnetic splitting:
• A nucleus with a spin greater than zero has a magnetic moment and
therefore interacts with a magnetic field.
• The requirements for the observation of magnetic splitting of Mössbauer
lines is that at least one of the nuclear states involved in the transition
possesses a magnetic dipole, and that a magnetic field is present at the
nucleus.
• Then the energy levels of the nuclear states split into 2nI + 1 sub-states.
Dr. D. Suresh
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452
Applied magnetic field
Magnetic splitting:
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453
Dr. D. Suresh
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Only one signal
88703 58876 two signals six signals 454
• The number of peaks in the Mössbauer spectra depends on the local
environments.
K4[Fe(CN)6]
Low spin complex
eg
t2g
Prussian Blue-Fe4[Fe(CN)6]3
FeIII4[FeII(CN)6]3
low spin complex

eg
4 FeIII
Dr. D. Suresh
t2g
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455
Two different Fe and hence two lines
[Fe(H2O)6]SO4 . H2O = FeSO4 . 7H2O
High spin complex
• Though ligands are in highly symmetrical ligands.
eg
• Due to the uneven distribution of ligands and the
presence of unpaired electrons lead to quadrupole
t2g
coupling.
• Thus the spectra will show two lines..
Dr. D. Suresh
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456
• Sodium nitroprusside is often
Na2[Fe(CN)5(NO)] used as a reference
compound for the calibration
Sodium nitroprusside
of Mössbauer spectrometers.
• Strong tetragonal distortion from Oh

symmetry due to the replacement of one of
the six CN- ligands by NO
• Thus gives rise to a significant quadrupole
splitting.
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[Fe(CO)5]
Strong tetragonal distortion

unsymmetrical ligand substitution
K3[Fe(CN)6]
• Ligands are in highly symmetrical ligands.
• Due to the uneven distribution of ligands (d5-high spin complex) and the
presence of unpaired electrons lead to quadrupole coupling.
• Thus the spectra will show two lines.
3- eg
Dr. D. Suresh
3K
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t2g
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[Fe3(CO)12]
(B)
Iron are in two different
environment, hence expected (A) (A)
to give two signals in
Mossbaurer spectrum.
Iron are in same
environment,
hence expected
to give only one
signal in
Mossbaurer
spectrum.
Dr. D. Suresh One signal as singlet (B) and another signal as
sureshvnr@gmail.com doublet (A) due to unsymmetrical ligand
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substitution (termnall and bridging CO ligands)
Number of peaks
• The number of peaks in the Mössbauer spectra depends on the local

environments.
• Only one spectral line is observed if only one type of Fe atom is present.
• If Fe atom contains different ligands, then accordingly the spectral line is
observed.
• If Fe atom has some unpaired of electrons, then the signal will split into
doublets due to nuclear quadrupole splitting.
• If it is recorded in presence of a magnetic field (having the nuclear
quadrupole effect or not), the 57Fe Mössbauer always shows six lines.
Dr. D. Suresh
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88703 58876
Dependency of Isomer shift:
• Chemical bonds between metal ion and ligands in coordination compounds
can be viewed as the result of the balance between -donation (s-electrons
from ligands are donated into s-orbitals of the metal) and d–p back
donation (d-electrons move from d-orbitals of the metal to empty p-orbitals of
the ligands).
• Both bonding mechanisms influence the isomer shift in the same direction,
but to different extent, depending on the nature of the ligands and thus on
the weight of the atomic orbitals of the metal and ligands participating in the
molecular orbitals (covalency effects).
• This is the reason why isomer shift scales for different compounds of the
Dr. D. Suresh
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same oxidation state often cover a broad range of values.
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Dependency of Isomer shift: Effect of -Back donation
• The isomer shift values become more positive on going from NO to H2O.
• The reason is that the strength of d–p back donation decreases causing an
increasing d-electron density residing near the iron center.
• Thus effecting stronger shielding of [Fe(CN)5Xn-](3+n)-

s-electrons by d-electrons, which
finally creates lower s-electron
density at the nucleus in the case
of H2O as compared to NO+.
• Isomeric shift value increased with

Dr. D.
strong Sureshdue to increase in
-bonding
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the s-electron density increases.
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Dependency of Isomer shift: Effect of Electronegativity
• The isomer shift increases with increase in electronegativity of the
substituents.
highest
Isomer shift
lowest
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Electronegativity
Isomer shift 57Fe Mössbauer Spectroscopy:
• The isomer shift of Fe2+ high spin

compounds are higher than that of the
Fe3+ high spin compounds.
• The isomer shift increases with increase
in electronegativity of the substituents.
The trend in isomer shift is,

Fe(II)–HS > Fe(III)–HS > Fe(II)–LS > Fe(III)–LS
highest lowest
Dr. D. Suresh
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• Lower
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symmetry, lower the isomer shift 464
Fe(II)–HS > Fe(III)–HS > Fe(II)–LS > Fe(III)–LS
highest lowest
Na2[Fe(CN)5(NO)]
Sodium nitroprusside
Reference material for
57Fe Mössbauer
Spectroscopy
Or
-Iron metallic powder
Fe – higher
oxidation state
higher the isomer
shift
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465
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High temperature – High spin system

(II)
High spin
Spin cross over
Spin cross over
(II)
Dr. D. Suresh
Low temperature – Low spin system
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Low spin Fe(II)–HS > Fe(II)–LS
119Sn Mössbauer Spectroscopy
excited state • The energy levels of 119Sn is exactly

opposite to 57Fe isotope.
• Hence the trends in isomer shift of
119Sn Mössbauer Spectroscopy will be
opposite to that of 57Fe Mössbauer
Spectroscopy
ground state
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Dr. D. Suresh
• The isomer shift decreases with increase in electronegativity of the
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substituents in
119Sn Mössbauer Spectroscopy:
• Increase in electronegativity of the substituent decreases the Isomer shift.
(Exactly opposite to 57Fe Mössbauer Spectroscopy)
• The isomer shift of Sn2+ compounds are higher than that of the Sn4+
compounds. (Exactly opposite to 57Fe Mössbauer Spectroscopy)
Sn4+ compounds Sn2+ compounds
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119Sn Mössbauer Spectroscopy:
Dr. 2D.
SnO Suresh
is used as reference material for 119Sn Mössbauer Spectroscopy
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57Fe and 119Sn Mössbauer Spectroscopy
Fe – higher oxidation state

higher the isomer shift
Sn – lower oxidation state

higher the isomer shift
Lower the symmetry, lower the isomer shift

Dr. D. Suresh
Tetrahedral < Square pyramidal < Octahedral
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121Sb, 127I and 129I Mössbauer Spectroscopy
121Sb and 127I 129I
8 transition lines
under
quadrupole splitting
for
121Sb, 127I and 127I
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8 transition lines under quadrupole splitting
CSIR June 2012 CSIR December 2015
CSIR June 2013
CSIR December 2014
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GATE 2010
GATE 2012
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Nuclear Quadrupole Resonance (NQR) spectroscopy
• Nuclear quadrupole resonance spectroscopy or NQR is a chemical analysis

technique related to nuclear magnetic resonance (NMR).
• In NQR the nuclei with spin I ≥ 1, such as 14N, 35Cl and 63Cu, also have an
electric quadrupole moment so that their energies are split by an electric
field gradient.
• NQR transitions of nuclei can be detected in the absence of a magnetic field,
and for this reason NQR spectroscopy is referred to as "zero Field NMR."
• Any nucleus with more than one unpaired

nuclear particle (protons or neutrons) will
have a charge distribution which results in
Dr.
an D. Suresh
electric quadrupole moment.
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Applications of NQR
• NQR has been used principally for investigating the electronic structure of
molecules
• Information regarding hybridization and the ionic character of the bond can
be determined by comparing the quadrupole coupling constant in atomic and
molecular state in the same nuclei
• Study of the structure of charge transfer complexes
• Detection of crystal imperfections, small imperfections destroy symmetry of
internal electric field, lead to splitting or broadening of NQR lines.
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Isomerism in Metal Complexes
Cis- or trans-
and
Dr. D. Suresh Fac- or mer
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Optical Rotatory Dispersion (ORD) and Circular dichroism (CD)
• The method of determining absolute configuration rests on three techniques:
• X-ray diffraction (XRD)
• Optical Rotatory Dispersion (ORO)
• Circular Dichroism (CD)
• It is very difficult to get single crystals for all the compounds, hence the other
two methods are practically possible to determine the absolute
configurations.
• Optical Rotatory Dispersion (ORD) and Circular Dichroism (CD) are very
useful in determining the absolute configuration of any complex.
• CD and ORD spectra can be used to identify two enantiomers of a chiral
Dr. D. Suresh
complex. Compounds with similar structures give similar ORD/CD spectra
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provided that they have the same absolute configuration
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• Circular Dichroism and Optical Rotatory Dispersion (ORD), an absorption
spectroscopy, uses circularly polarized light to investigate structural aspects
of optically active chiral molecules.
Oriented in only one

directions
Randomly oriented
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Linear polarized light occurs when

the electric field vector oscillates
in only one plane.
In circularly polarized light, the electric

Dr. D. Suresh field vector rotates around the
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Light can be circularly polarized in two directions: left and

right.
If it rotates clockwise, it is right If it rotates anti-clockwise, it is left
circularly polarized (RCP) circularly polarized (LCP)
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The superposition of LCP and RCP light of the same
88703 58876 amplitude produces linearly polarized light 481
• If the plane-polarized light is passed through a sample of chiral molecule
(having different refractive indices for the individual isomers) the plane of the
polarization has been rotated through an angle , given by
ηl−ηr
=
λ
ηl, ηr = refractive index of left and right rotating medium
 = wavelength of light used
• The specific rotation of a chemical compound []T is defined as the
observed angle of optical rotation. when α plane-polarized light is passed
through a sample with a path length of 1 decimeter and a sample
concentration of 1 gram per 1 mL.
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• A negative value of specific rotation
[]T means levorotatory rotation (S or

) and a positive value means
dextrorotatory rotation (R or ).
Optical Rotatory Dispersion (ORD):
• Optical Rotatory Dispersion (ORD) involves measuring the variation of
optical rotation with wavelength. (plot of  Vs )

• There is abrupt reversal of rotation in the vicinity of absorption band.
• If the complex is levorotatory (), the ORD curve falls to a minimum, rises
rapidly to a maximum and then slowly falls.
• If Dr.
the D. Suresh
complex is dextrorotatory (), the effect is reversed for the ORD curve
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rising first to a maximum, then falling etc
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Cotton effect:
• The Cotton effect is the characteristic change in optical rotatory dispersion in
the vicinity of an absorption band of a substance.
Positive Cotton effect in which the Negative Cotton effect in which the
change in rotation is from negative to change in rotation is from positive to
positive as the wavelength is changed negative as the wavelength is changed
-configuration -configuration
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Cotton effect:
• If two compounds give electronic transitions that show Cotton effects that
are the same (either both positive or both negative), the compounds have
the same chirality or optical configuration.
Circular dichroism (CD):
• Although ORD was used extensively at one time because of simpler

instrumentation, circular dichroism (CD) is currently much more useful.
• The circular dichroism (CD) refers to differential absorption of left and right
circularly polarized light, L  R.

L and R are the molar absorption
• CD curve is a plot of  Vs 
Dr. D. Suresh coefficients for left- and right-
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Circular dichroism (CD)
• The CD spectrum of chiral molecules suggest that -isomer shows positive

deflections while -isomer shows negative deflections in CD spectrum which
also corresponds to the sign of Cotton effect.
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Circular dichroism (CD)
• Circular dichroism is usually
observed in the vicinity of an
absorption band: a positive Cotton
effect shows a positive peak at the
absorption maximum and a negative
effect shows a negative peak.
• This simple spectrum makes CD
more selective and easier to
interpret than ORD; CD has become

Dr.method
the D. Suresh
of choice for studying
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chiral 58876
complexes. 487
Summary of Unit IV
UV-Visible Spectroscopy:
Atomic Term symbols:
Number of microstates for given electronic configuration

x = number of electrons;
y = number of subshell
! = Factorial
Number of microstates for given term symbol = (2L+1)(2S+1)
Spin selection rule: Laporte selection rule:
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UV-Visible Spectroscopy: Summary of Unit IV
Orgel diagram
d1, d4, d6 and d9
d2, d3, d7 and d8

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Summary of Unit IV
UV-Visible Spectroscopy:
Tetragonally distorted complexes: the Jahn–Teller effect
charge transfer (CT):
eg
t2
g
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Summary of Unit IV
IR Spectroscopy:

1H NMR:
Protons Chemical shift
M-H – 5 to – 20
M-CH3 1 to 4
M-Olefin  3 to 4
M- (C5H5) (Cp)  4
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M-(C6H6)  4 to 7
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M=CH2 491
19F, 11B, 31P
Summary of Unit IV
NMR:
(2naIa + 1) (2nbIb + 1)...

Dr. D. Suresh Fluxional behavior
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NMR for paramagnetic complex
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492
Summary of Unit IV
EPR:
no. of splitting line = (2naIa + 1) (2nbIb + 1)…..
• First step is to find the oxidation

state of the transition metal.
• Then the number of d-electrons and
the number of unpaired electrons.
• Then by using the formula,
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Summary of Unit IV
Mössbauer Spectroscopy:
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The End
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Problem 1
Tungsten hexacarbonyl [W(CO)6] reacts with sodium tetrahydroborate (NaBH4)
to give an anionic product. The tetraethylammonium salt has empirical
composition C18H21NO10W2. Its 1H NMR spectrum includes a triplet, intensity
ratio 1:6:1, at - 22.5 ppm, with a separation between the outer peaks of 42 Hz.
What can you deduce about the anion? (I for H and W = 1/2)
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Answer 1
• C18H21NO10W2 – This is the empirical formula of the complex which contains
both the cationic and anionic part.
• It is given that cationic part is tetraethyl ammonium which is nothing but
N(C2H5)4+ whose formula is C8H20N
• If subtract this cationic moiety formula from the complex will give you the
formula for anionic moiety.
• So, C18H21NO10W2 – C8H20N4 = C10HO10W2
• [C10HO10W2]- – This is the anionic part of the complex, which we have to find
out the structure.
• If we look at the starting material, it contains CO, the end product should
also contains CO. By the above anionic formula, we see 10 Carbon and 10
oxygen, so there could be 10 CO in the product. So now the formula
Dr. D. Suresh
becomes [(CO)10W2H]-
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Answer 1
• By NMR, it is confirm that there is Metal-hydrogen bond (M-H whose
chemical shift is from 0 to – 30 ppm). So there should be W-H bond too
• Now if we look at the anionic formula, [(CO)10W2H]-, we have two W and 10
CO and only 1 H. So structure should be, [(CO)5W-W(CO)5H]-
This is a stable complex, since

12 (2W) + 20 (10 CO) + 1 (H) + 2 (W-W) + 1
(-ve charge) = 36 electrons.
That is 18 per W.
Matching the structure with NMR:

W–H is there whose chemical shift value is at -22.5 ppm.
It appears as a triplet. Here two different W is there. W (I = 1/2) so, 2nI
Dr. D. Suresh
+ 1, (221/2) +1 = 3 (triplet).
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Problem 2
When Fe(CO)5 is refluxed with cyclopentadiene compound A is formed which
has the empirical formula C8H6O3Fe and a complicated 1H NMR spectrum.
Compound A readily loses CO to give compound B with two 1H-NMR
resonances, one at negative chemical shift (relative intensity one) and one at
around 5 ppm (relative intensity five). Subsequent heating of B results in the
loss of H2 and the formation of compound C. Compound C has a single 1H-
NMR resonance and the empirical formula C7H5O2Fe. Compounds A, B, and C
all have 18 valence electrons: identify them and explain the observed
spectroscopic data.
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Problem 2
Hint: A, B, and C all have 18 valence electrons
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Answer 2
• Fe(CO)5 refluxed with C5H5 (Cp) to afford product A whose empirical formula
is C8H6O3Fe. Hence the product should contain cyclopentadienyl ligand and
carbon monoxide (CO). The empirical formula should be (C5H5)(CO)3Fe.
• Cp can adopt various Hapticity like 5, 3, and 1.
• It is given that A obeys 18 electron. So we have to find out the Hapticity
value. X (Cp) + 6 (3 CO) + 8 (Fe) = 18; X = 4. But Cp can not act as 4.
Hence it should be 3 and a negative charge should be ideal.
• So A is [(3-C5H5)(CO)3Fe]-. This is confirmed by 1H NMR which is a
complicated one which corresponds to the 3-C5H5 moiety.
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(Cp) + 6 (3 CO) + 8 (Fe) + 1 (H) = 18
Answer 2
• A, [(3-C5H5)(H)(CO)3Fe], upon heating losses CO and gave B which also
obeys 18 electron rule.
• NMR of B shows two signals one at negative chemical shift with 1 H,
indicating a metal-hydrogen that is Fe-H and another one singlet with 5H
indicating the Cp ring undergoes a change from 3 to 5.
• So the structure of B is [(5-C5H5)(CO)2FeH]
Dr. D. Suresh
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5 (Cp) + 4 (2 CO) + 8 (Fe) + 1 (H) = 18
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Answer 2
• B, [(5-C5H5)(CO)2FeH], om refluxing looses H2 to give C whose empirical
formula is C7H5O2Fe. So two equivalents of B reacts to give C 2(C7H5O2Fe).
That is 2[(5-C5H5)(CO)2Fe)].
• The compound C shows only one signal with around 5 ppm which is
corresponds to Cp.
• Hence the structure is
10 (2 Cp) + 8 (4 CO) + 16 (2 Fe) + 2 (Fe-Fe) = 36; That is 18 per Fe
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A B C
Problem 3
Treatment of TiCl4 with 4 equivalents of NaCp gives a single organometallic
compound (together with NaCl by-product). At room temperature the 1H-NMR
spectrum shows a single sharp singlet; on cooling to - 40°C this singlet
separates into two singlets of equal intensity; further cooling results in one of
the singlets separating into three signals with intensity ratios 1:2:2. Explain
these results.
room temperature
shows a single sharp singlet
- 40°C
two singlets of equal intensity
Dr. D. Suresh one of the singlets separating

Further cooling
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88703 58876 ratios 1:2:2. 504
Answer 3
Clearly this compounds is an example for a
fluxional molecule. Now we have to find out how
the Cp ligands are coordinated to Ti.
• At room temperature, all Cp rings are same. Hence only one signal.
• If we assume Cp in 5 mode,
• the total electron is 20 (4 Cp) + 4 = 24 electron. This is

not a stable complex.
• the total electron is 16 (5 + 5 + 3 +3 Cp) + 4 = 20
Dr. D. Suresh electron. This is not a stable complex.

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Answer 3
• the total electron is 12 (4 Cp) + 4 = 16 electron. This is

a stable complex.
room temperature
shows a single sharp singlet
All Cp rings are exchanged fastly
- 40°C two singlets of equal intensity

2 different types get exchanged
one of the singlets separating into

Further cooling
Dr. D. Suresh three signals with intensity ratios
1:2:2.
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Problem 4
When Mo(CO)6 is refluxed with cyclopentadiene compound A is formed which
has the empirical formula C8H5O3Mo and an absorption in the IR spectrum at
1960 cm-1. Compound A can be treated with bromine to yield B or with Na/Hg
to give compound C. There are absorptions in the IR spectra of B and C at
2090 and 1860 cm-1, respectively. Compounds A, B, and C all have 18 valence
electrons: identify them and explain the observed spectroscopic data.
Dr. D. Suresh
sureshvnr@gmail.com
Hint: A, B, and C all have 18 valence electrons
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Answer 4
• Mo(CO)6 is refluxed with cyclopentadiene to give A with formula C8H5O3Mo.
The product should contain Cp and CO. Hence the if we split the formula
into Cp and CO we get, (C5H5)(CO)3W.
• Hint is that A is a 18 electron. To find out the Hapticity, X (Cp) + 6 (3 CO) + 6
= 18; So X = 6. Cp can not exhibit 6. Hence 5 and a negative charge is
possible. Bur IR data (1980 cm-1 for CO) says it is neutral complex. Hence, A
is dimer (5-C5H5)(CO)3Mo-Mo(CO)3(5-C5H5).
10 (2 Cp) + 12 (6 CO) + 12 (2 Mo) + 2 (Mo-Mo) = 36;

That is 18 per Mo
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Answer 4
• Compound A (5-C5H5)(CO)3Mo-Mo(CO)3(5-C5H5), a dimer, which can
under go oxidative addition with bromine (Br2) by cleaving the metal-metal
bond to give compound B.
• So compound B is (5-C5H5)(CO)3MoBr.
5 (Cp) + 6 (3 CO) + 6 (Mo) +

1 (Br) = 18
• Compound A (5-C5H5)(CO)3Mo-Mo(CO)3(5-C5H5), a dimer, which can

under go reduction with Na/Hg by cleaving the metal-metal bond to give
compound C.
• So compound B is [(5-C5H5)(CO)3Mo]-.
5 (Cp) + 6 (3 CO) + 6 (Mo) +

Dr. D. Suresh
sureshvnr@gmail.com 1 (-ve charge) = 18
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Answer 4
IR = 1960 cm-1 IR = 2090 cm-1 IR = 1860 cm-1

A B C
Anionic complex
Neutral complexes with terminal CO with terminal CO.
Hence higher the CO stretching frequencies Hence lower the CO
stretching frequencies
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CSIR December 2014
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GATE 2009
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The End
Dr. D. Suresh
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88703 58876

Inorganic Spectros

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Inorganic Spectros

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Organometallics, Non-Metals and Inorganic Spectroscopy

E-mail Id: sureshvnr@gmail.com

• Since evils new from evils ever grow,

Physical Methods in Inorganic Chemistry

IR and Raman spectroscopy: Vibrational modes – Group frequencies of infrared

ESR spectra of metal complexes: Hyperfine splitting and A parameter – g

Mossbauer Spectroscopy: Basic Principles – Spectral parameters and

Spectroscopic methods for optically active complexes: Optical rotatory

Dr. D. Suresh R. S. Drago

Electromagnetic Radiation and its Interactions with Matter

C = velocity of light in vacuum (3  108 m sec-1)

Dr. D. As frequency () increases, energy (E) of light increases

“பார்ப்பது கண் அளவு”

• X-rays, gamma rays cause the ionization of atoms/molecules and hence

Etot = Eelec + Evib + Erot + Espin + Etrans + Enuc

• The occupancy of the electronic S3

Absorption process • In non-radiative process, the energy is

The relative magnitude energy levels are in the order of

electronic energy levels (S)

S1 v3 vibrational energy levels (v),

Ground state Excited state Triplet

Energy of Excited state Singlet > Energy Excited state Triplet

For free radical, containing unpaired electrons...!

Dr. D. Suresh Ground state

• When molecules absorb energy in the microwave region the rotational

valence shell electrons are get promoted to higher energy levels.

• These transition give rise to a spectrum are called Electronic absorption

spectroscopy or absorption spectroscopy

• The excited state molecules relaxed to ground state by emitting either

fluorescence or phosphorescence in the UV-Visible region.

• The emitted radiation is analyzed by the spectrophotometer and the

graphical plot of intensity of emission as a function of frequency or

wavelength is appropriated called as fluorescence or phosphorescence

Vibrational and rotational relaxation

Intersystem crossing (ISC) (reversal of

• The intensity () of UV-Vis spectroscopy is having very large magnitude in

• Beer–Lambert law fails to maintain a linear relationship between dilution and

• Over an extremely small concentration range known as the critical micelle

Principal quantum number (n) Angular quantum number (l)

• The term symbol for particular atomic state is given by,

S= total spin angular momentum

Step 1: To calculate spin multiplicity (2S + 1)

spin (small “s”) of the electron is +1/2 () or -1/2 ()

number of unpaired electrons

In this case, only one electron so both s and S = 1/2

In this case, d1 configuration

Azimuthal quantum number (l) can have value from +l to 0 to -l

J = L – S when the subshell is less than half filled

In this case (d1), less than half filled,

So the ground state term symbol is 2D3/2

Step 1: To calculate spin multiplicity

spin (small “s”) of the electron is +1/2 () or -1/2 ()

number of unpaired electrons

The spin multiplicity is given by, 2S + 1

• L can have value of zero or any positive number.

L = (+2  2) + (+1  2) + (0  2) + (-1  2) + (-2  1)

J = L – S when the subshell is less than half filled

In this case (d9), more than half filled,

So the ground state term symbol is 2D5/2

Step 1: To calculate spin multiplicity

number of unpaired electrons

The spin multiplicity is given by, 2S + 1