Contents

Introduction Theory of NMR Chemical Shift

Factors Influencing Chemical Shift Important Facts about Chemical Shift

2 2 5
7 9

Coupling Constant

10

Introduction
NMR was discovered by Bloch and Purchell in 1946. NMR spectroscopy involves the absorption electromagnetic radiation in the radiofrequency region.

As the name suggests, NMR spectroscopy involves the transition of a nucleus from one spin state to another with the absorption of electromagnetic radiation by spin active nuclei, when they are placed in a magnetic field. Spin active nuclei are the nuclei having nuclear spin not equal to zero.

The electromagnetic radiations used in NMR spectroscopy have very long wavelength (107 to 108) and have extremely low energy. These radiations are radio frequency waves which are not energetic to affect the electronic, vibrational or rotational energy of the molecule. However, they are able to interact with the nuclei of certain atoms which are exposed to a strong magnetic field, hence the name Nuclear Magnetic Resonance Spectroscopy.

Theory of NMR
When a proton is placed in an external magnetic field, its magnetic moment can be aligned in two ways:

i) With the field (parallel alignment) ii) Aligned against the field (anti-parallel alignment) It is possible to induce transitions between these two states i.e. a proton processing in the aligned orientation can pass into the opposed orientation by absorbing energy.

Also, it can come back from the high energy, anti-parallel alignment by losing energy. This transition from one energy state to another is called flipping of a proton.

The amount of energy which is required to flip the proton from one state to another depends upon the strength of the external magnetic applied. Stronger the field, greater will be the tendency of the nuclear magnet to remain lined up with it and higher will be the energy required to flip the proton to a higher energy state.

If E is the energy difference between the two states, then

E = 2Bo v = 2Bo / h

where:

h is the Planck's constant is the magnetic moment Bo is the external magnetic field

The complete study of NMR spectra deals with the study of following points:

i) The number of signals: The number of different kinds of protons in the molecules.

ii) The position of signals: The electronic environment of each kind of proton, thus indicates their nature i.e. aliphatic, aromatic, primary, secondary or tertiary.

iii) The intensities of the signals: The number of each type of proton.

iv) The splitting if signal into several peaks: The environment of a proton with respect to its neighbouring protons.

A compound for NMR spectroscopy must be a liquid or a solid that can be placed in solution. The usual-solvents for NMR spectroscopy are deutrochloroform (COCl3), deutroacetone (CD3COCD3), deutriumoxide (D2O) etc.

The area of higher field strength is called upfield while that of lower field strength is called downfield.

Chemical Shift
When a molecule is placed in a magnetic field its electron are made to circulate and thus generate a secondary magnetic field called induced magnetic field which may either reinforce or oppose the applied magnetic field. In case the induced field opposes the applied field, the field felt by the proton is diminished, such a proton is said to be shielded. This shielded proton requires a stronger magnetic field to produce an absorption signal (as compared to a native proton) and thus is said to absorb upfield.

On the other hand, if the induced field reinforces the applied field, the field felt by the proton is increased, such a proton is said to be deshielded. A deshielded proton requires a lower applied field to produce an absorption signal and thus is said to produce/absorb downfield.

The shifts in the position of NMR signals arising from shielding or deshielding by electrons are referred to as Chemical Shift.

Chemical shifts are measured with the reference to some fixed standard Tetramethylsilane (TMS), (CH3)4Si is the standard in the proton magnetic resonance spectroscopy.

The choice of TMS as the standard has following advantages:

i) TMS is chemically inert. ii) It is miscible with almost all organic substance iii) It is highly volatile and is readily removed from the system.

The most commonly used scale is the (delta scale) for chemical shift. The position of the Tetramethylsilane (signal) is taken as 0.0 ppm as reference.

Most chemical shifts have values of between 0 and 10. A small value represents a small downfield shift and a large value represents a large downfield shift.

NMR spectra are displayed on charts having the magnetic field strength versus energy absorption. A small amount of TMS is mixed with the sample as standard and the NMR spectrum is recorded.

The proton -NMR spectrum of a molecule thus gives information about:

i) The number of signals or peaks which enables us to know about the kinds of protons present in a molecule.

ii) The intensities of peaks which tell us about the number of protons of each kind that are present.

iii) Position of peaks which tell us about the electronic environment of each kind of proton.

Factors Influencing Chemical Shift

i) Inductive effect: A proton is said to be deshielded if it is attached to an electronegative atom or group. Greater the electro negativity of the atom, greater is the deseeding caused to the proton. Consider the following compounds: (i) CH3-CH2-F b a (ii) CH3 -CH2-Cl b a

Two signals are expected for each of the two compounds. Deshielding for protons 'a' in compound (i) is more than that for similar protons in compound (ii). As the distance from the electronegative atom increases, the deshielding effect due to it decreases. Protons in 'b' have comparatively higher value of S.

ii) Van der Wall's deshielding: In the overcrowded molecules, it is possible that some proton may be occupying sterically hindered position. Electron group of the bulky group will tend to repel the electron cloud surrounding the proton. Thus, such a proton will be deshielded and will resonate higher value of than expected in the absence of this effect.

iii) Anisotropic effect: The deshielding effect on protons attached to C=C is higher than that can be accounted for by the inductive effect alone. Aldehydic and aromatic protons are much more deshielded. Alkyne protons appear at relatively low value of . The value of (chemical shift) in each case can be justified by explaining the manner in which -electrons circulate under the influence of the applied field.

iv) Hydrogen bonding: If a hydrogen atom exhibits the property of hydrogen bonding in a compound, it will get deshielded due to strong electronegative

atoms attached to it. As a result, absorption is shifted downfield.

Important Facts about Chemical Shift

i) If local environment are otherwise equivalent, the more the number of hydrogen on a carbon, the greater is the shielding and more up-field is the absorption signal.

Thus, the order of shielding is:

CH < HCH < HCH H

ii) Electronegative atoms such as O2, N2 and halogens deshielded the proton and so the absorption takes place downfield.

iii) The -electrons of an aromatic ring, >C=C< and >C=O have strong deshielding effect on the attached proton.

Thus, the order of deshielding is:

CH

<

>>

C=CH

iv) The carbonyl group (>C=O) deshields a proton and adjacent carbon. Thus the proton is the framework O=C-C-H gets deshielded. Similarly, benzylic (Ar-C-H) and allylic (>C=C-C-H) protons are deshielded to a smaller extent.

v) H-bonding deshields the protons concerned.

vi) Strongly electropositive atoms such as silicon increase the electron density near the proton and thus, shield it. As a result, the absorption takes place upfield in such cases.

Coupling Constant
The distance between the peaks in a multiplet is referred to as a coupling constant. It is denoted by the symbol J and is expressed in the units of cps or Hertz.

This constant is a measure of the magnitude of splitting effect. Unlike the chemical shifts, the J values are independent of the applied magnetic field but depend markedly on the molecular structure.

Conditions of coupling constant for special types of protons:

i) Case of geminal protons: These are the protons present on the same carbon atom. In this case, J = 0-20 cps, depending upon the bond angle. At 120o, its value is 0 while at 105o, it rises to 20 cps.

ii) Case of vicinal protons: These are the protons located on the adjacent carbon atoms. In this case, J = 2-18 cps, depending upon the dihedral angle. Thus, proton with anti-conformation have J = 5-14 cps.