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Nuclear Magnetic Resonance Spectroscopy

Basic Principles

H3C
4.5 4.0

CH3 O

3.5

3.0

2.5

2.0

1.5

1.0

0.5

Dilip D. Dhavale Department of Chemistry University of Pune, Pune – 411 007 ddd@chem.unipune.ernet.in
2.60 2.50 2.40 2.30 2.20 2.10 2.00 1.90 1.80 1.70 1.60 1.50 1.40 1.30 1.20 1.10 1.00 0.90 0.80

0.0

Spectroscopy
Study of the interaction of light with matter Light: Visible part of a large range of Electromagnetic Radiation having corpuscular as well as wavelike properties. Energy E = hν ( h = Planck’s constant 6.62 x 10 –27 erg/sec)
Cosmic and UltraGamma Rays Violet Visible Infra-Red Near Far
8000 104

Microwave

Radio

A0 10-4

1000

2000

4000

107

1014

Nuclear Transition

Electronic Transitions

Molecular Vibrational Transitions

Molecular Rotational Transitions

Nuclear Spin Transitions

Energy cal/mole 1014 – 1010

100 – 35 K

~28.5 K

10-2 – 10-6

Spectroscopy
Sample at Equilibrium

Radiation Relaxation

Observation
Excited State Spectrum

UV-Visible: Presence of chromophoric system/conjugation in the molecules IR Spectroscopy: Presence of Functional Groups in the molecules H NMR Spectroscopy: The number of different types of Hydrogens in the molecules The relative numbers of different types of Hydrogens in the molecules The electronic environment of different types of Hydrogens in the molecules The “neighbours and a neighbours” of a functional group
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These spectroscopic techniques are mutually complimentary and a combination of these three-along with a Mass Spectroscopy form a powerful device in the determination of structures of organic molecules.

History of NMR Spectroscopy
In 1945 - The phenomenon was simultaneously discovered by two groups: Purcell, Torrey and Pound at Harvard University: Paraffin Bloch, Hansen and Packard at Stanford University: Water In 1950 – The first NMR spectra of ethyl alcohol was recorded by Arnold, Dharmatti and Packard. In 1952 – The two discoverers (Bloch and Purcell) were awarded the First Nobel Prize in NMR (Physics). In 1991 – The second Nobel Prize in NMR (Chemistry) was awarded to Richard Ernst for discoveries of advanced methodologies. In 2002 – The third Nobel Prize in NMR (Chemistry) was awarded to Kurt Wuthrich for determination of structures of Biomolecules in solution by NMR. Nobel Prize awaited to Paul Lauterbur for Magnetic Resonance Imaging

Behavior of Magnetic Nuclei
For nuclei with spin I = ½ Two possible orientations as per equation 2I + 1 Randomly oriented nuclear spins of equal energy in the absence of any magnetic field

ElectromagneticRadiation in R F range with energy E =∆ Ep _ 1 2 Ho ∆EP + 1 2 Precisely oriented nuclear spins in the presence of Magnetic field +1 2 _ 1 2

In NMR, we are measuring the energy required for the flipping of the nucleus

Nuclear Spin
• A nucleus with an odd atomic number or an odd mass number has a nuclear spin. • The spinning charged nucleus generates a magnetic field.

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Magnetic Properties of Nuclei
l

Nucleii spin + charge

Spinning charged particle is a magnet

The spinning of positively charged particle produces: (1) Spin angular momentum or Spin quantum number (I) (2) Magnetic moment (µ) along the axis of spin (3) Electric quadrupole moment (Q) (as a result of non-spherical distribution of nuclear charge)

The angular momentum of spinning nucleus is described in terms of spin quantum no.I

The spin quantum no. I is a characteristic constant of a nucleus, and is dependent on the number of protons and neutrons. In general three rules apply to the nuclear spins. 1) Nuclei with odd mass number and odd or even no. of protons have half – integral spin such as 1/2, 3/2, 5/2 etc.

2)

Nuclei with even mass number and odd no. of protons have integral spin such as 1, 2, 3

1)

Nuclei with even mass number and even no.of protons always have zero spin (Due to pairing of oppositely directed spins in the nucleus)

Nuclear Properties of Important Nuclei - I
Nucleus
1 2

No. of Proton 1 1 5 6 6 7 7 8 8 9 14 15

No. of Neutron 0 1 6 6 7 7 8 8 9 10 15 16

Mass No. 1 2 11 12 13 14 15 16 17 19 29 31

Spin No. (I) 1/2 1 3/2 0 1/2 1 1/2 0 5/2 1/2 1/2 1/2

Natural % Abundance 99.98 00.0156 81.17 98.80 01.108 99.635 00.365 99.95 00.037 100.00 04.70 100.00

H H B C C N N

11 12 13 14 15 16 17

O O F

19 29

Si P

31

Requirements of nuclei to be NMR active
Three important characteristics:  Nuclei should have Spin no. I > 0 and magnetic momemtum µ > 0  Nuclei should have even charge distribution that is nucleus should be spherical in shape so as Q = 0.  Nuclei should have high % of natural abundance
H, 13C, 19 F and 31 P nuclei have I = 1/2 and µ > 0 These nuclei are spherical in shape (even charge distribution) and Q = 0 So observed by NMR technique. 1 H, 19F and 31P have high % abundance
1

C and 16O nuclei are also spherical in shape Q = 0; but I = 0 and µ = 0 So non-magnetic and not observed by NMR
12

H, and 14N nuclei have I > 0; µ > 0 and Q > 0 Nuclei are ellipsoidal prolate in shape, so no even charge distribution. So difficult to study by NMR
2

Ellipsoidal oblate 35 Cl

Ellipsoidal prolate

Basic NMR Equation
For proton spin no. I = ½. Therefore, there are (2I + 1) two possible orientations. The energy of orientation is a product of magnetic moment µ and strength of the applied Field Ho (E = µHo).
Aligned against the field High − energy orientation
E = hν

At resonance: hν = 2 µ Ho
θ
E2 = + µ HO

ν= 2µHo / h The equation is rewritten as

E = 2 µ HO

ν= γ Ho /2π
Where γ = 2π.µ / h.I It is a proportionality constant between µ and I. Also called as Gyro magnetic ratio. It is constant for a particular nuclei but different for different nuclei.

θ
HO

E1 = − µ HO

Aligned with the field Low − energy orientation

The behaviour of a nuclear magnet in a magnetic field
HO

ωo
Nuclear magnet Precessional orbit H

µ

Two ways of doing NMR experiment
ν = γ Ho / 2π

Sweeping – change magnetic field Keep constant frequency

Change the frequency Keep magnetic field constant

External Magnetic Field
When placed in an external field, spinning protons act like bar magnets.

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Nuclear Properties of Important Nuclei -II
Nucleus Spin quantum number Magnetic moment (µ) Gyromagnetic ratio (γ) Resonance frequency (MHz at a Field of 1 T) 42.577 6.536 4.575 13.660 10.705 3.076 4.315 5.772 40.055 8.460 17.235 Relative sensitivity at constant field 1.000 0.009 0.02 0.165 0.016 0.001 0.001 0.029 0.834 0.079 0.066 Natural abundance (%) Quaderpole moment, Q

1 2

H H B B

1/2 1 3 3/2 1/2 1 1/2 5/2 1/2 1/2 1/2

2.792 0.857 1.8007 2.6880 0.702 0.403 -0.282 -1.8930 2.627 -0.5549 1.131

2.675 0.411 0.288 0.858 0.673 0.193 -0.271 -0.363 2.517 -0.531 1.083

99.98 0.0156 18.83 81.17 1.108 99.635 0.365 0.037 100.0 4.70 100.0

0.003 0.111 0.036 0.02 -0.004 -

10 11 13 14 15 17

C N N

O F

19 29

Si P

31

The NMR Spectrometer

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The NMR Graph

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Interpretation of NMR Spectrum
NMR Spectra is analysed on the basis of following parameters  Integration  Chemical shift  Coupling constant  Rate processes
9.5

9.0

O H3C OEt

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8.0

7.5

7.0

6.5

6.0

5.5

5.0

4.5

4.0

3.5

3.0

2.5

2.0

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1.0

0.5

0.0

4.5

4.0

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3.0

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2.0

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NMR Signals
• The number of signals show how many different kinds of protons are present. • The location of the signals show how shielded or deshielded the proton are. • The intensity of the signal shows the number of protons of that type. • Signal splitting shows the number of protons on adjacent atoms.

Integration
The process of excitation in NMR involves the flipping of the nucleus. This process of transition and the probability of the transition is same for all the protons, irrespective of the electronic environment. As a result, the area under the NMR resonance is proportional to the number of hydrogens which that resonance represents. In this way, by integrating the different NMR resonance, information regarding the relative numbers of chemically distinct hydrogens can be found. The integrals will appear as a line over the NMR spectrum. Integration only gives information on the relative number of different hydrogens, not the absolute number.
9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 0.93 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 2.40 2.45 2.08

O H 3C CH3
6 mm

2.42 2.43

6 mm
0.91 0.94

4 mm
2.0 1.5 1.0 0.5

2.5

Intensity of Signals
• The area under each peak is proportional to the number of protons. • Shown by integral trace.

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Integration: Determination of keto – enol ratio

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Chemical Shift: Shielding of a proton in a magnetic field
Basic equation of NMR is ν = γHo/2π wherein resonance frequency is simply a function of applied magnetic field and gyro magnetic ratio. If so, then all the protons in a molecule should resonate at one place- NMR of no value to organic chemists!!!!!

What is true?
electron current

The resonance frequency is, to a small extent, dependent on its Electronic Environment Making NMR Useful to Structure Determination

Induced magnetic moment opposing the applied magnetic field

H1
ν= γHo/2π Where, Ho = strength of the applied magnetic field experienced by the nucleus. And Ho = H1 (1 − σ ) where H1 is the actual strength of the applied field and σ is the shielding constant. More the electron density – more is the shielding Less the electron density – more is the deshielding

Chemical Shift
The difference between the positions of absorption of reference standard and that of a particular proton or a group of protons

CH3-CH2-OH

5

4

3

2

1

0

Reference peak is kept at zero of the chart What is reference ?

Requirements for a reference standard in NMR
A good standard should meet the following requirements: • It should be chemically inert (non-reactive). • It should give a single sharp line. • It should be magnetically isotropic. • It should have unique line position. • It should be Miscible with organic solvents. • It should be readily volatile to allow recovery of the compound.
H H H CH3 CH3

TetraMethylSilane
H 3C

C Si

Silicon is more electro-positive than carbon. Therefore, pushes electron density towards carbon and thus to hydrogenmaking methyl protons strongly shielded.

Units of Chemical shift
 Chemical shifts are expressed in Hz.  Chemical shifts expressed in Hz are proportional to the applied magnetic field HO/oscillator frequency.  For example, In CH3CH2OH 60 MHz CH3 60 Hz CH2 216 Hz OH 300 Hz This can be calculated by the equation: Frequency of X proton (Hz) in A instrument Osc. frequency of A in Hz 100 MHz 100 Hz 360 Hz 500 Hz 300 MHz 300 Hz 1050 Hz 1500 Hz

X

Osc. frequency of B in Hz

(major difficulty in calculating chemical shift as variety of instruments)

Units of Chemical shift
Chemical shift are also expressed in δ (ppm)

δ=

Shift in frequency from TMS (Hz) Frequency of spectrometer (Hz)

X 106

δ is dimensionless and is NOT PROPORTIONAL to Ho or Osc. frequency. δ value is same in all the different instruments Universal scale in NMR Higher the value of chemical shift in Hz or δ − deshielded is the proton. Lower the value chemical shift in Hz or δ − shielded is the proton.

General regions of chemical shift
Aliphatic alicyclic β -Substituted aliphatic Alkyne α -Monosubstituted aliphatic α -Disubstituted aliphatic Alkene Aromatic and heteroaromatic Aldehyde 10 Deshielding 8 7 6 5 4 Shielding 3 2 1 0 High field

9

Low field

Solvents for NMR
A satisfactory solvent should be  It should be chemically inert  It should not contain protons  It should be non – polar and should have low – boiling point  It should have low viscosity
D3COOD D3CCOCD3 D3CCN C6D6 CDCl3 CD2Cl2 D3C-SO-CD3 F3C.COOD 2.02, 11.53 2.05 1.95 7.20 7.25 5.35 2.50 10-11

Chemical Equivalence
 Chemically

equivalent protons O O CH3 X H 3C O Y CH3 H3CO OCH3 Z

H 3C

X, Y, and Z have one set of equivalent protons.
 Chemically

non-equivalent protons

CH3CH2Cl 2 signals

CH3CH2OCH2CH3 2 signals

CH3CH2OH 3 signals

Number of Signals
Equivalent hydrogens have the same chemical shift.

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Parameters that affect the Chemical shifts
 Electron Withdrawing Inductive Effect

 Diamagnetic anisotropic shielding and deshielding effect  Electron donating and withdrawing mesomeric (resonance) effect

Chemical shift: Electron Withdrawing Inductive effect
R CH3 R CH2 R R3 CH R C CR2 CH3 CH3 CR
O

0.9 1.3 1.7 1.6 2.1 2.3

R CH2 I

3.2

C-CH3 0.9 N-CH3 2.3 O-CH3 3.3 R 2C CH R 5.3 2.5 7.25 RCO2H 10 - 12 R2NH ROH ArOH 2-4 1-6 6-8

R CH2 Br 3.5 R CH2 Cl 3.7 CH3 OH CH3 OCOCH3 CH3 OR O RC-H 9.7 3.3 3.6 3.0

R C C H H

CH3

Electron withdrawing inductive effect is one of the parameter that affects the chemical shift Stronger the electron withdrawing group - more is the deshielding
Protons attached to O, N, S are resonating anywhere between 1 to 15 δ. The position depends on a) substrate b) solvent c) concentration d) temperature. The best method to detect these protons is to re-run the spectra on addition of drop of D2O, wherein these protons will change their position

Carboxylic Acid Proton, δ10+

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Magnetic Anisotropic Effect
Carbon-Carbon double bond and triple bond (The influence on induced magnetic moments of neighbouring bonds)

Circulation of electrons perpendicular to Ho
Shielded Region

Shielded Region

+
Deshieded Region

+
H H R1 R
Deshieded Region

R H

Ho

Deshieded Region

Deshieded Region

+
Shielded Region
Olefinic Protons at δ 4.5-6.0

Induced Magnetic Field

Shielded Region
Acetylenic Protons at δ 2.5-3.0

+

Magnetic Anisotropic Effect
Ring Current Effect in Benzene Ring

Benzene protons at δ 7.25

Magnetic Anisotropic Effect
(Induced by magnetic moments of neighboring bonds)

Ho

Ho

Ho

H δ 8.99 C H δ 6.42 H δ 5.48 O H CH3

O

CH3 δ (Ring) 8.14 - 8.64 δ (CH3) − 4.25 δ 3.53 H OH HO H δ 3.75

H

H

δ − 0.42 H

H δ 1.42

δ (Ring) 7.27; 6.95 δ (CH2) − 0.51 H H H H H H H H3CO O H H3CO O O H H3CO OCH3 δ 6.49 H O OCH3 H3CO δ 8.04 H O

H H

H H

H H

H

H H

O

O

O

H

H

δ (H outer) 9.28 δ (H inner) −2.99

Chemical Shift: Resonance effect
 Electron

donating resonance effect increases electron density at the carbon and in turn to hydrogen – Shielding of proton. Electron withdrawing resonance effect decreases electron density at carbon and in turn to hydrogen – Deshielding of proton.
R 5.40 6.38 H H β 3.85 H α OCH3 H β H H α OCH3
H H H

5.28

H

5.85 H β α

C O

CH3

H α H β H

C O

CH3

6.40 H

α-H-deshielded due to -I effect β -H-shielded due to +M effect

α -H-deshielded due to small -I effect β -H-deshielded due to strong -M effect

Chemical Shift: Resonance effect
ED ED ED EW EW EW

Substituent OCH3 OH OAc NH2 NMe2

Ortho - 0.43 - 0.5 - 0.2 - 0.75 - 0.64

Meta - 0.09 - 0.14 - 0.02 - 0.24 - 0.10

Para - 0.37 - 0.40 - 0.63 - 0.60

Substituent NO2 CHO CN

Ortho + 0.95 + 0.58 + 0.27

Meta + 0.17 + 0.21 + 0.11

Para + 0.23 + 0.27 + 0.30

Spin-spin Coupling
9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 0.93 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 2.40 2.45 2.08

O H3C C H2 CH3

2.42 2.43 0.91 0.94

2.5

2.0

1.5

1.0

0.5

• Three groups of non-equivalent hydrogens, therefore three signals
are expected. • These signals are split into peaks due to the spin-spin interactions of non-equivalent protons. • Spin-spin interaction occurs between adjacent non-equivalent protons only.
J

Coupling constant J is always expressed in Hz J is Independent of Operating frequency. Multiplets are symmetric about the mid point = δ

J

Mutually coupled protons have identical coupling constant J

Spin-Spin Coupling
• Nonequivalent 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.

Types of Coupling
Three types of coupling in NMR  Geminal Coupling [1,3 coupling]: Coupling between nuclei on the same carbon (Two bond coupling) Vicinal Coupling [1,4 coupling]: Coupling between nuclei on the adjacent carbon atom (Three bond coupling) Long range Coupling [1,5; 1,6- coupling] Coupling between nuclei separated by more than three carbon atoms (Coupling between nuclei separated by more than three bonds)
4 H
2

H1 H3
1 H C 2

C

3 C

4 C 5H

H1 2 3 C C

Coupling constant ‘J’ always expressed in Hz It is independent of applied magnetic field/Operating frequency

Rules of coupling (First Order Analysis) Three rules govern the number and nature of multiplets in NMR
 Equivalent protons do not couple with each other.  Maximum No. of Lines = (2na.Ia + 1) x (2nb. Ib + 1) x (2nc. Ic + 1)……. na, nb, nc = number of neighboring non-equivalent nuclei Ia,Ib, Ic = spin numbers of the respective nuclei. In case of 1H, 19F and 31P nuclei, spin no. = ½. Therefore, Maximum no. of lines = (na + 1) x (nb + 1)….  When the multiplicity is produced by a group of equivalent nuclei with I = ½, the intensities of the different lines are given by the coefficient of expression (X + 1)n where n = number of interacting nuclei. These rules are valid if ∆ν/ J > 6 (where ∆ν is a frequency difference between coupled protons)

Structure
HA C C

Spin States

Signals

No adjacent proton

HA C

HB C

One adjacent non-equivalent proton

HA C

HB C HB

Two adjacent nonequivalent protons

HA C

HB C HB HB

Three adjacent non-equivalent protons

Pascal’s Triangle Relative intensities of first order multipletes
n = number of equivalent nuclei 0 1 2 3 4 5 6 7 8 1 1 8 1 7 28 1 6 21 56 1 5 15 35 70 1 4 10 20 35 56 1 3 6 10 15 21 28 1 2 3 4 5 6 7 8 Relative Intensity 1 1 1 1 1 1 1 1 1

Coupling of proton with neighboring nuclei

1,1,2-Tribromoethane
Nonequivalent protons on adjacent carbons.

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Doublet: 1 Adjacent Proton

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Triplet: 2 Adjacent Protons

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Splitting for Isopropyl Groups

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Values for Coupling Constants

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Spectrum for Styrene

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Mechanism of Spin-Spin Coupling
HB C2 C1 HA HO HA C1 C2 HB HA

HA
∆E1

HA
∆E ∆E2

HA HA
∆E – ∆E1 = ∆E2 - ∆E

HA
8

HB C2 C1 HA
Jab Nuclear Spin 4 +1/2 J Electron Spin -1/2 J 4

HA C1 C2 HB
HA in the absence of HB (s) HA in the presence of HB (d)
Line due to HB

Line due to of HB

J Vicinal always +ve

Geminal Coupling
HA C HB

HA

HB ∆E2 Low field Due to of HB High field Due to of HA

HA HO

HB

If HB is aligned to Ho-drop in ground state and increase in exited state energy This effect is opposite to that observed in vicinal coupling Geminal coupling constant is always negative

The splitting of the signal from the methyl protons in ethanol by spin-spin interaction with the protons of the methylene group
Splitting arising from spin-spin coupling with the protons of Total Spin the methylene group -1 Orientations 1

0 Unperturbed signal +1 Spin arrangements of the methylene protons

2

1
Line positions in 200 MHz NMR

HO-CH2-CH3
In ethanol, methyl appears at 1δ as a triplet with J = 6 Hz.

2

+1J
1

-1J
1

206

200

194

The splitting of the signal from the methylene group protons in ethanol by spin-spin interactions with the protons of the methyl group
Splitting arising from spin-spin coupling with the protons of the methyl group
Total spin Orientations -3/2 -1/2 1 3

Unperturbed signal

+1/2

3

+3/2

Spin arrangements of the methyl protons

3 -1/2 +1/2 1

1 3

Lines in 200 MHz

HO-CH2-CH3
In ethanol, methylene protons appear at 3.5 δ as a quartet with J = 6 Hz

+3/2 J 703 700 697

-3/2 J

1

709

691

Ha Hc Hd

12 lines for Ha

First Order Analysis (ddt)
16

X

V1 –V2 = Jad V1 – V4 = Jab V1 – V6 = Jab

Hb

Hd

Jab

8

15 Hz

8

Splitting due to Hb

Jac
4Hz

4 4Hz 1 2

10Hz

4

4

10Hz

4 4Hz 1 2

Splitting due to Hc Splitting Due to Hd

4Hz 1 2 1

4Hz 1 2

4Hz 1 1

4Hz

Jad

1

First Order Multiplet Analysis
Multiplets are reported starting with the largest coupling first, e.g. td J = 8.0 and 3.0 Hz implies a triplet with a J = 8.0 Hz and a doublet with J = 3.0 Hz, which is very different from a doublet, J = 8.0 Hz and a triplet J = 3.0 Hz.
X X
3 Hz

X

H

H

H

H H

H

X H

H

Spin System
 If

∆ν/J ratio is large (greater than 8), the interacting nuclei are weakly coupled. They are well separated, Designated as AM or AX.
O O Ha 6.45 Hb 7.72
 If

In 100 MHz ∆ν/J = 772 – 645 = 127 Hz J = 10 Hz ∆ν/J = 127/10 = 12.7

∆ν/J ratio is small (less than 6), the interacting nuclei are strongly coupled. Designated as AB
6.0 Hb Ha 5.9

Cl

S

Br

In 100 MHz ∆ν/J = 600 –590 = 10 Hz J = 4 Hz ∆ν/J = 10/4 = 2.5

Such a collection of set insulated from further coupling form a spin system

Intermediate analysis: 3 < ∆ν/ J Second order analysis: ∆ν/ J < 3

AB Multiplets: Effect of ∆ν / J ratio

AB Multiplet Analysis

Non – equivalence due to restricted rotation
19

F spectrum of BrCF2-CCl2Br
Five lines at − 120 °C

Only one line at 25 °C

Three possible conformers

Both are mirror images

Br Cl F Cl F
Cl Fa

Br

Br Br Fb Br Fb Cl

Cl Fa

Br Both F nuclei equivalent Singlet

Cl

Both F nuclei are non equivalent Five lines

J. D. Robbert and P. M. Nair 1959

Non – equivalence due to restricted rotation
In case of compounds wherein methylene group is attached to the carbon having three different groups- the two methylene protons are non – equivalent.

R2

R1 H a C C R R3 H b

Three possible conformers
Ha R3 Hb R2 R1 R Ha R1 Hb R3 R2 R Ha R2 Hb R1 R3 R

Some Nonequivalent Protons
a H C C H c

c H OHa dH Hb

Hb

CH3 H aH Cl Cl Hb

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AB Multiplet Analysis

Some approximate J values
Alkanes and Cycloalkanes
H C H C H J = 0 - 10 Hz H Ja,a = 7 - 10 Hz Je,e = 0 - 5 Hz Ja ,e = 0 - 7 Hz H H H H

Alkenes
H H J = 11 - 18 Hz Trans H H H J = 0 - 3 Hz SP2 Geminal H J = 11 - 18 Hz SP3 Geminal J = 5 - 14 Hz Cis
J = 7- 9 Hz Ortho J = 1 - 2.5 Hz Meta

H

H

H

Aromatics
H H H H

H J = 8 - 11 Hz

H H J = very low Para

Factors affecting Vicinal Coupling Constant (3J)
The magnitude of 3J (sign is always positive) depends in essence upon four factors
 The

dihedral angle φ, between the C-H bonds under consideration (a).
H H

H φ

H

 The C,C bond length, Rµν (b).
Rµ,ν b

a

 The H-C-C valence angles, θ and θ’ (c)

H θ c

θ' H

 The electronegativity of the substituent R on the H-C-C-H

H d

H R

Karplus Correlation
Relationship between dihedral angle (φ) and coupling constant for vicinal protons

Dihedral Angle Axial - axial Axial - equatorial Equatorial - equatorial 180° 60° 60°

Calculated J (Hz) 9 1.8 1.8

Observed J (Hz) 8 -14 1-7 1-7

Rate Processes
NMR of CH3CH2OH ( with trace of acid/base impurity)

CH3-CH2-O-H

H+ H
+

CH3-CH2-O

H H

H H+ CH3-CH2-O H

NMR of pure ethanol

Effect of High Oscillator Frequency
Chemical shift in Hz is proportional to the oscillator frequency. Coupling constant J in Hz is not proportional to the oscillator frequency. As a result, NMR spectra are more resolved at high operating frequency. For example:The NMR of compound BrCH2CH2CH2 shows: δ 3.70 (t, J = 7 Hz), 3.55 (t, J = 7 Hz), 2.27 (quin, J = 7 Hz)
60 MHz instument 3.70 = 222 Hz 3.55 = 213 Hz
300 MHz instrument 3.55 = 1065 Hz 3.70 = 1110 Hz

∆ν / J = 9/7 =1.3
1 229 222 222 2 1 215 1 220 213 213 220 215 229 205
1117 1103 1072 1058

2

1 205

1 1117

2

1 1103

1 1072

2

1 1058

1110

1065 1065

∆ν / J = 45/7 =6.5

1110

As ∆ν/J ratio increases - NMR is more resolved Interpreted by first order analysis

AMX Spin System

ADVANCES IN MRI
Magnetic Resonance Imaging (MRI) has reached a high level of maturity and has established itself as the diagnostic modality of choice in almost all neurological system disorders, joint diseases, Mediastinal and heart pathologies, work-up of abdominal and pelvic malignancies and evaluation of vascular system of the body.