NMR SPECTROSCOPY

NMR
NMR INTRODUCTION
 All atomic nuclei can be characterized by a nuclear spin
quantum number, I. I can be ≥ 0 and any multiple of ½.
 Nuclei with I = 0 do not possess nuclear spin and
consequently are termed ‘NMR silent’.
 All nuclei with I ≠ 0 possess spin, charge, and angular
momentum P, resulting in a nuclear magnetic moment
 µ = γP
 Where γ is the magnetogyric ratio of the nucleus.
NMR
NMR QUANTUM CHEMISRY
 I = the nuclear spin quantum number

NMR QUANTUM CHEMISRY
 For Nuclei of: I= Example Odd Mass Half
Integer 1
H, 13C
 Even Mass/Even Charge Zero 12
C, 16O
 Even Mass/Odd Charge Integer 2H, 14N

 If I = 0, NMR Inactive
 If I ≥1, Quadrupolar (non-spherical nuclear charge
distribution)
NMR QUANTUM CHEMISRY
 I is quantized producing (2I + 1) discrete values of angular
momentum, mI.
 mI = I, I -1, …-I

NMR CONCEPT –SPIN STATE


NMR CONCEPT –SPIN STATE
NMR Concepts – Relaxation

 Once excited to the higher energy state by an rf pulse, the spins will return to their initial

equilibrium condition by means of two relaxation mechanisms, T1 and T2.

 T1 relaxation (longitudinal): Spin-lattice relaxation occurs by transfer

 of energy to the surroundings (heat); dipolar coupling to other spins. Results in recovery of

Mz to

 63% of original value.

 T2 relaxation (transverse):Spin-spin relaxation occurs by redistribution

 of energy among various spins of the system. Results in recovery of Mz to 37% of original

value.

 T2 ≤ T1

 T1 and T2 are routinely equivalent for most NMR experiments.

 NMR Linewidths ~1/ T2 for spin ½ nuclei

 Inorganic/Organometallic Linewidths -
NMR Concepts – Relaxation
NMR INSTRUMENTATION
Chemical shift
 different local chemical environments surrounding any
particular nuclei causes them to resonate at slightly different
frequencies. This is a result of a nucleus being more or less
shielded than another. This is called the chemical shift (δ).
One factor that affects chemical shift is the changing of
electron density from around a nucleus, such as a bond to an
electronegative group. Hydrogen bonding also changes the
electron density in 1H NMR, causing a larger shift.
Chemical shift

 The shift in the position of PMR signals resulting through

shielding and DE shielding by circulation of electrons in chemical
bonds is called the chemical shifts. • Protons in most of the
organic compounds absorb over a range of 700 Hz (cps) at a
field strength of 14100 Gauss. At this field strength protons
absorb at a frequency of about 60 x 106Hz. • The shielding and
DE shielding of protons by electrons produce very small change
in the strength of the applied magnetic field. These small
changes in the magnetic field strength cannot be determined
accurately. Therefore absolute position of the PMR signal cannot
be obtained. Therefore, chemical shifts of protons are expressed
in Hz or (cps) with reference to a particular standard.
Chemical shift
 The frequency and the strength of the magnetic field are related by
the equation • The most commonly used reference for PMR
spectroscopy is tetramethylsilane (TMS) (CH3 )4Si. It is chosen as a
reference compound for the following reason:- 1. It has 12
equivalent protons, therefore a very small amount of the TMS
produces a large single sharp signal. 2. TMS protons absorb at a
field much higher than the protons in most of the organic
compounds. This is due to the reason that silicon is more
electropositive than carbon. 3. It is chemically inert and is also
highly volatile (b.p. 300 K). Therefore, after the spectrum has been
scanned, the precious sample can be recovered by the removal of
TMS by evaporation. 4. It is highly miscible with most of the organic
solvents.
Units of Chemical Shif

 The commonly used unit is parts per million (ppm). • It is

dimensionless and are independent of the field strength or
oscillator frequency of the instrument. • It is the function of
the chemical environment of the protons in the organic
molecule.
Scales of the Chemical Shift

 It express in two scales. (i) The d (delta) scale (ii) The 

(tau) scale  = 10 - d On the d scale the position of TMS
signal is taken as 0.0 ppm and most of the chemical shifts
have d values between 0-10. Shielded protons have low d
values whereas DE shielded protons have large d values.
CHEMICAL SHIFT

 Paramagnetic contribution arises from non-spherical electron distribution (nuclei with

non-s orbitals). It is the dominating factor of chemical shift for all nuclei other than
protons.
 Magnetic anisotropy of neighboring bonds and ring currents – π electrons of
triple bonds and aromatic rings are forced to rotate about the bond axis creating a
magnetic field which counteracts the static field.
 Electric field gradients are the result of strongly polar substituents. The distortion of
the electron density alters the chemical shift.
 Hydrogen bonding can lead to a decrease in electron density at the proton site
resulting in a chemical shift to higher frequency. Hydrogen bonded protons exhibit
shifts that are highly dependent on temperature, solvent, and concentration.
 Solvent effects are often exploited to separate overlapping signals of interest in a
spectrum. Large changes in chemical shift can be observed for solvents that can
selectively interact with one portion of a molecule (acetone for it’s carbonyl group,
and benzene for its ring currents)
Chemical shifts of different types of protons

 Types of proton Chemical ppm

shift 

1. Cyclopropane  0.2 9.8
2. Primary R–CH3 0.9 9.1
3. Secondary R2.CH2 1.3 8.7
4. Tertiary R3CH 1.5 8.5
5. Aromatic Ar-H 6.0-8.5 1.5-4.0
FACTOR AFFECTING
CHEMMICAL SHIFT

 Inductive effects
 The proton chemical shifts increases as the
electronegativity of the atom attached to the
carbon atom bearing hydrogen increases.
Thus is due to -I effect of the electronegative
atom.
 The electron density around the proton
decreases which causes deshielding. Thus,
higher the electronegativity higher the
deshielding and hence higher the d value of the
chemical shifts.
Inductive effects

Compound Elemen Electronegativit Chemical shift

t y

CH3–C F 4.0 d- 4.26

t- 5.74
CH3–O O 3.5 d-
3.5
t-
3.40
Greater the number of halogen atoms, greater in the
DE shielding

CH3 CH2C CHC

Cl l2 l3
d d d
3.0 5.30 7.27
2. HYDROGEN BONDING

 Protons which exhibits hydrogen bonding (e.g. — OH and —

NH2 protons) show variable absorption position over a wide
range (0.5 - 5.0 ppm) since H– bonding decreases the
electron density in the O—H bond, therefore, the proton
involved in H– bonding gets deshielding.
 Further stronger the hydrogen bond more deshielded is the
proton. The extent of H– bonding depends upon
concentration, temperature and nature of the solvent. Thus in
concentrated solutions, H– bonding predominates and H–
bonded protons appear in the range 4-5.
ANISOTROPIC EFFECT
ANISOTROPIC EFFECT
SPIN –SPIN COUPLING

 Every set of equivalent protons gives are PMR signal. But

the spectra of most of the organic compounds are much
more complicated. For example : 1, 1, 2- tribromoethane
(CH2Br-CHBr2).
 This compounds contains two kinds of protons and hence its
PMR spectrum to show only two peaks. But spectra of this
compound show five peaks.
SPIN SPIN COUPLING
SPIN SPIN COUPLING
 Spin-spin or scalar coupling is the result of Fermi contact
interaction between electrons in the s orbital of one nucleus
and the nuclear spin of a bonded nucleus.
 The magnitude of coupling depends on the degree of
electron orbital overlap. The s-character of the orbitals relies
heavily on the hybridization of the nuclei involved.
SPIN SPIN COUPLING
SPIN –SPIN COUPLING
 Nuclei in a molecule are affected by the spins systems of
neighboring nuclei. This effect is observed for non-
equivalent nuclei up to 3 bond lengths away and is termed
spin-spin coupling or J coupling
SPIN SPIN COUPLING
APPLICATION OF NMR

1.Determination of Empirical Formulae.

 The transition of a proton from one spin state to the other is fundamentally the
same irrespective of the chemical environment of the proton. For this reason
the transition probability and hence intensity of absorption is the same for
every proton in the molecule, provided certain aspects of experimental
technique are observed. The intensity of absorption of a given proton is
determined by measuring the area under the absorption band which it gives
rise to in the n. m. r. spectrum. Thus, if the total area enclosed by the nuclear
magnetic resonance spectrum of a solution, containing a known concentration
of a compound of unknown structure, is compared with the area of a solution
containing known concentration of a compound of known structure, it is
possible to derive the percentage of hydrogen in the former compound. To do
this, the two determinations. must be carried out under precisely the same
conditions and it must be established that the result is independent of the
amount of radio-frequency power used in both determinations*.
Determination of the Classes of Protons
in a Molecule. The Chemical Shift.
 Since various commercial spectrometers operate at different field
strengths, it is not convenient to express the chemical shift in
c./sec. Instead, these separations are converted to field
independent units in the following way. The separation between
the tetramethylsilane absorption line and that of a proton in the
reference sample is defined as a positive quantity LI c./sec. if the
latter occurs at lower fields. (In the rare cases in which a sample
absorption occurs at higher fields Ll is taken as negative.) One
convenient field independent expression of the chemical shift is
then given as Lt. 106 !5-- spectrometer frequency' This is known
as the !5 scale and on this scale tetramethylsilane is at zero
parts per million.
. The Number of Protons in a
Given Class. Intensities.
 Having established the various classes present in a
molecule, the next problem is to count the number of protons
in each class. This is done by determining the intensities of
the absorptions arising from various classes of protons by
integrating the absorption bands. As discussed above, the
area under the absorption bands will be proportional to the
number of protons which give rise to the absorption, and for
a single molecular species this means that the intensities of
the various absorption bands arise from different classes of
protons in each class
The Sequence of Groups in Molecules.
Electron Coupled Spin-Spin Interaction.
 The absorption bands arising from single protons or from
groups of equivalent protons (i. e. protons with exactly the
same chemical shift) frequently exhibit well defined fine
structure when examined under high resolution. Fig. 2 shows
the spectrum of acetaldehyde in which it can be seen that
the aldehyde proton gives rise to a quartet and that the
protons of the methyl group give rise to a doublet. It should
be further noticed that the quartet is symmetrical, the spacing
of the quartet components is the same as that of the doublet
Applications to the Elucidation of Relative
Stereochemistry and Conformation.
 Both the chemical shift and the magnitude of spin-spin
coupling are critically'dependent on geometrical factors. In
cases in which this dependence is understood it is possible
to use chemical shift and coupling constant data to derive the
relative orientations of protons in molecules and, hence
determine the relative stereochemistry of groups. It is
important to realize that many organic molecules are
dynamic equilibrium mixtures of vanotts conformations and
that in almost all of such systems the observed nuclear
magnetic resonance parameters have values which
correspond to time averages over these conformations. T