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Engineering Chemistry III Prof. K. M.

Muraleedharan

NMR - Basic principles


Subatomic particles like electrons, protons and neutrons are associated with ‘spin’- a
fundamental property like charge or mass. In the case of nuclei with even number of
protons and neutrons, individual spins are paired and the overall spin becomes zero.
However, there are many cases such as 1H and 13C, where the nuclei possess a net spin,
which is important in Nuclear Magnetic Resonance (NMR) Spectroscopy. A set of rules
to determine the overall spin a nucleus is given below.

• When there are even number of protons and even number of neutrons in the
nucleus, the net spin is equal to zero.
• When there are odd number of neutrons and odd number of protons in the
nucleus, it will have an integer spin (i.e. 1, 2, 3)
• If the sum of the number of neutrons and the number of protons is odd number,
the nucleus will have a half-integer spin (i.e. 1/2, 3/2, 5/2).

These rules can be summarized in terms of atomic mass and atomic number as shown
below.

I Atomic Atomic Examples


Mass Number
Half- Odd Odd 1H (1/2)
integer NMR active

Half- Odd Even 13C (1/2)


integer
Integer Even Odd 2H (1)

Zero Even Even 12C (0) Not NMR


active

Nuclei are charged and those with a net spin would generate a magnetic dipole
along the spin axis. The magnitude of this dipole is given by the nuclear magnetic
moment μ, which is give by
μ = γ I h / 2π ..................................(1)
where I is the spin quantum number (with values ½, 1, 3/2 etc.) and

Indian Institute of Technology Madras


Engineering Chemistry III Prof. K. M. Muraleedharan

γ = Gyromagnetic ratio, which is a characteristic constant for individual


nuclei.
In Nuclear Magnetic Resonance Spectroscopy, we study the behavior of magnetic nuclei
in presence of an external magnetic field. Quantum mechanics tells us that a nucleus of
spin = I can have 2I+1 orientations with respect to an external magnetic field. Since the
main aim of this chapter is to illustrate the use of NMR in the study of aromaticity, we
will focus on the magnetic properties of 1H and see what special information does 1H
NMR spectroscopy provide when this nuclei (1H) is part of an aromatic system.
A nuclei such as 1H with spin = ½, can orient in two ways (2 x ½ + 1 = 2) with
respect to the external field. Of these, the spin state represented as +1/2 (or α state) is of
lower energy where as the one represented as -1/2 (or β state) is of higher energy. The
former reinforces the applied field and the latter opposes it. The energy difference
between the two spin states is proportional to the applied field and can be written as
ΔE = hν = hγB0/2π ..................................(2)
B

where, h = Plank’s constant,


γ = Gyromagnetic ratio which is a characteristic constant for individual
nuclei,
B0 = strength of the magnetic field at the nucleus
B

From equation (2), it is clear that a radiation of frequency ν = γB0/2π possess the
B

right amount of energy to effect a transition from lower energy α state to higher energy β
state. Absorption of energy takes place only with a certain combinations of field strengths
and radio frequencies during which the system is said to be in a state of resonance.

For proton, γ = 2.675x108 T-1s-1


If the NMR spectrometer is equipped with a magnet with a field of 7.046T,
2.675 x 108 T-1S-1 x 7.046 T
ν = γ B0/2π = = 300 x 106 Hz = 300 MHz
2 x 3.1416

Indian Institute of Technology Madras


Engineering Chemistry III Prof. K. M. Muraleedharan

This can be pictorially represented as shown below:

Energy
Spin state I = -1/2 (β )

I = 1/2

Spin state I = +1/2 (α )

Field strength B0

NMR experiments can be performed in one of the following ways,


i) keep the external magnetic field strength constant and vary the frequency of
radiation to see an absorption
ii) keep the radio frequency constant and slowly vary the field strength until the
splitting of spin states corresponds to the energy of radio wave.

In new versions of instruments, instead of Continuous Wave (RF) sweeping, an intense


radiofrequency pulse is used to excite all nuclei simultaneously and their individual
absorptions determined using Fourier transform methods

Shielding and Deshielding


So far we were considering the magnetic moments generated by the spinning
nucleus and its interaction with an external field. However, in realty, nuclei are
surrounded by electrons which also generate small local magnetic fields (Bloc) as they
circulate. These local magnetic fields can either oppose or augment the external magnetic
field. If the field created by the electron oppose the external field, nuclei ‘experience’ an
effective field which is smaller than the external field and it is said to be SHIELDED. If
the field created by the electron augments the external field, nuclei ‘experience’ an
effective field which is larger than the external field. It is said to be DE-SHIELDED.

i.e. Beff = Bo - Bloc


B

This can be represented as Beff = Bo( 1 - σ )

Indian Institute of Technology Madras


Engineering Chemistry III Prof. K. M. Muraleedharan

σ – magnetic shielding or screening constant; depends on electron density.


Equation (2) can now be written as
ΔE = hν = hγ Bo( 1 - σ )/2π ..................................(3)
Equation (3) shows that magnetic field ‘felt’ by individual nuclei varies depending upon
their chemical environment; ΔE and hence the energy of the radiation required to excite
them differ consequently.

Diamagnetic and paramagnetic anisotropy


Two effects that originate from electronic delocalization in aromatic systems are
1) External field induces a flow (current) of electrons in π system – ring current effect
2) Ring current induces a local magnetic field with shielding (decreased chemical shift)
and deshielding (increased chemical shifts) zones. This is the basis of diamagnetic
anisotropy in aromatic systems which can be diagrammatically represented as shown
below.

In the case of compounds with unpaired electrons, paramagnetism associated with


the net spin overrides the diamagnetic effects and lead to a different type of magnetic
effect (vide infra)

Chemical shift and δ scale


As mentioned, effective magnetic field at individual nuclei vary depending upon
their chemical environment. Radiofrequency required to excite them also will be
different under different external field strengths. This means that if we take NMR spectra
of a compound using instruments of different field strengths, peaks appear at different
positions and it would be difficult to compare them without applying corrections for

Indian Institute of Technology Madras


Engineering Chemistry III Prof. K. M. Muraleedharan

differences in absorptions. To avoid this problem, a different system, based on ‘chemical


shift’ is often used. In this, we use a reference compound in our experiments. It is
generally tetramethylsilane, which is unreactive with other organic compounds, volatile,
and gives an absorption which is relatively shielded in comparison with most of the
protons important to organic chemists. Solvent used in NMR experiments should not
contain 1H due to interference. Deuterated solvents such as CDCl3, DMSO-D6 etc. are
generally used in modern instruments.
Now let us see what are chemical shift and δ scale.
At first, the absorbance frequencies of the standard and our sample are measured.
The latter is then subtracted from the former and then divided by the frequency of the
standard. This gives a number called the chemical shift (δ). Let us assume that in a given
magnetic field (external field), the ‘standard’ absorbs at 300,000,000 Hz (300
megahertz), and our sample absorbs at 300,000,300 Hz. The difference between our
sample and the standard is 300 Hz, and we take 300/300,000,000 = 1/1,000,000 and call
it 1 part per million (or 1 ppm). If we examine the same sample in a stronger magnetic
field where the reference comes at 500,000,000 Hz (or 500 megahertz), the frequency of
our sample will increase proportionally, and will come at 500,000,500 Hz. The
difference in this case would be 500 Hz. But if we divide this difference by 500,000,000
ie., 500/500,000,000, we will get 1/1,000,000, = 1 ppm! So, chemical shift values remain
the same irrespective of the instruments (field strengths). Although we did these
calculations manually, all these are done automatically in the computer associated with
the NMR spectrometer. A correlation of radiofrequencies and δ values and their relative
positions with respect to TMS (standard) is presented below.

Indian Institute of Technology Madras


Engineering Chemistry III Prof. K. M. Muraleedharan

A representative NMR spectra is given below

H H
H H H C C Br
H C C Br H H
H H

Shielding and deshielding zones in Aromatic systems

Due to the magnetic field generated by the circulating electrons, hydrogens which
lie in the plane of the ring experiences a deshielding effect as shown below (A). At the
same time those situated above and below the plane experience shielding, as the
magnetic lines of force are opposite in direction with respect to the applied field. Similar
effect, but to a lesser extent, can be seen in simple olefins (B), aldehydes etc.

Applied
magnetic
field H H

B0
δ 7-8 ppm δ 5-7 ppm

A B
Illustrative examples:
Chemical shift positions of hydrogen atoms which are placed in the shielding and
deshielding zones of aromatic systems are given below.

Indian Institute of Technology Madras


Engineering Chemistry III Prof. K. M. Muraleedharan

Bridge head protons at -0.5 δ

Outer protons at 6.9-7.3 δ Inner protons 0.00 δ Outer ring protons at 8.14-8.67 δ
H
Outer protons 7.6 δ CH3 protons at -4.25 δ
H
H H H H H H3C
H CH3
H
[14]-annulene

H H Outer protons at ~ 9 δ Ha
H H 2 Hb
Inner protons at ~ -3 δ Ha at -0.3 δ
3
Hb at 5.1 δ
H H H H H1
4 H1 & H7 at 6.4 δ
H H H7
H H H H H2-H6 at 8.5 δ
5 6

H H
H H

[18]-annulene

Antiaromatic systems

Antiaromatic systems are paratropic. That is, they are able to sustain a
paramagnetic ring current, which lead to shielding of outer ring protons and deshielding
of inner protons (opposite to that of aromatic compounds which show diamagnetic
effect). Examples presented below demonstrate the behavior of magnetic nuclei situated
in an antiaromatic environment.
1) At -170oC, inner protons of [12]-annulene comes at ~8 ppm and outer protons comes
at ~6 ppm which is characteristic of antiaromaticity. Above -150oC, all protons are
magnetically equivalent showing conformational flexibility. Above -50oC, it rearranges
to a bicyclic system as shown below.

above -50oC

[12]-annulene

Indian Institute of Technology Madras


Engineering Chemistry III Prof. K. M. Muraleedharan

2) At -130oC [16]-annulene is paratropic with four central protons at 10.56 δ, and


twelve outer protons at 5.35 δ. Above -50oC, all protons are magnetically equivalent
showing conformational flexibility

H H
H H in solution

Nonaromatic
[16]-annulene

3) As discussed previously, the locked form of [14]-annulene show significant


aromatic character, with outer protons resonating at 8.14-8.67 δ and CH3 protons coming
at -4.25 δ. However, the dianion of this compound is antiaromatic which is evident from
the paramagnetic anisotropic effect seen in its NMR.

Outer ring protons at 8.14-8.67 δ Outer ring protons at -3 δ


H H
CH3 protons at -4.25 δ CH3 protons at 21 δ

H3C H3C
CH3 CH3
reduction

Indian Institute of Technology Madras

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