PROTON

NUCLEAR MAGNETIC RESONANCE

SPECTROSCOPY

PNMR
 SPECTROSCOPY
• Spectroscopy can be used to elucidate the
structure of a molecule

• Types of spectroscopy:
– IR spectroscopy
– Mass spectrometry
– NMR
NUCLEAR MAGNETIC RESONANCE
SPECTROSCOPY (NMR)
• The nuclei of protons (1H) and carbon-13 (13C),
and certain other elements and isotopes,
behave as if they were tiny bar magnets
• When placed in a magnetic field and irradiated
with radio frequency energy, these nuclei
absorb energy at frequencies based on their
chemical environments
• NMR spectrometers are used to measure
these absorptions
 NMR Spectroscopy
• Much more information can be obtained
• Like IR, molecules should be relatively simple
• Equivalent hydrogen atoms
• Nuclei flip in a magnetic field of the correct
strength
• Position in ppm (0 for TMS internal standard)
• Integration used to determine number of H’s
• Shifting of peaks
• Splitting of peaks
 Basics
• The nuclei of certain
elements and isotopes have
a property called “spin”,
behaving as if they were
spinning about an axis
– For example, 1H and 13C
– Since they are positively
charged, they act as tiny
magnets, and therefore
interact strongly with any
applied magnetic field.
• The spinning motion is
random, but when the The parallel spin
nuclei are placed in a state is lower in
very strong magnetic energy than the
field, they align such anti parallel spin
that their own field is state.
either parallel to or
against the external field
 Matter/Energy
Interactions
• What happens when a sample absorbs Rf energy opposed
to field
(radio frequencies) in an NMR experiment?

nuclei previously aligned in a Rf

strong external magnetic field
are “flipped” against the field (100’s MHz)
aligned
with field

 B0
{B0 = external magnetic field}
• If energy is supplied in the form of radio
frequency electromagnetic radiation, the
lower energy spin state absorbs that
radiation and “spin-flips” to the higher
energy orientation.
– NMR spectrometers are used to measure the
absorption

spin flip
-1/2
E = h
E
(absorb photon)

1/2 Bo
 Spin State Energy
Differences
vs. Magnetic Field Strength
 spin
state

randomly
oriented nuclei E E
(no magnetic field) 200 MHz 400 MHz
for 1H for 1H


 spin
Energy state
High Field NMR
• increased sensitivity
0 4.7 9.4 • increased resolution

Magnetic field strength, B0 (Tesla)

• Each nucleus experiences a slightly different
magnetic field based on their electronic
environments.
– Since the amount of energy required for a spin-
flip is directly proportional to the magnetic field
experienced by each nucleus, every nucleus
absorbs slightly different amount of RF radiation.

 E E
E






0
Bo
 “PRECESSING
NUCLEUS”
S opposed
to field

N Z
Rf
N
Y
B0
aligned X
S
with field

nucleus “flipping” nucleus precessing

(over-simplification!) (like a spinning top)
 Electron Shielding
Around Nucleus

 B0  Blocal

 Bi

a bare nucleus (H+) electrons generate an electron density partially

feels the full effect of induced field (Bi) shields the nucleus from
the external field (B0) which opposes B0 B0 so it “feels” Blocal
 Continuous-Wave (CW) NMR
Spectrometers

• The magnetic field is varied as the

electromagnetic radiation is kept at a
constant frequency

• Different nuclei absorb the

electromagnetic energy based on their
chemical environment and produce peaks
in different regions of the spectrum

10
Fourier Transform (FT) NMR
Spectrometers

• Greater sensitivity and higher resolution

than CW
• The sample is placed in a constant (and
usually very strong) magnetic field
• The sample is irradiated with a short pulse
of radio frequency energy that excites
nuclei in different environments all at once
 Basics
• Those nuclei “relax” and
fall back to their original,
lower energy spin
orientations, thereby
emitting that energy over
time.
• The process is called “free-
induction decay”, producing
data in the form of an
interferogram

• This signal is
converted to a
spectrum by the
FT
 Basics
• Now the time domain data must be converted into
the frequency domain, using the Fourier
Transformation (FT).

• The values along the x-axis are “chemical shifts”

in units of ppm, related to the frequency of
radiation absorbed, and therefore the magnetic
field experienced by each nucleus.
 400 MHz NMR Spectrometer
400 MHz Advance System

computer

electronic
controls

super-
conducting
magnet
 400 MHz
Superconducting
Magnet
• magnetic field strength •
9.4 Tesla (94,000 gauss)
400 MHz is the frequency used NMR sample tube and holder
descend into center of magnet
for proton detection in this field

Keep metal (ferromagnetic)

objects, pacemakers, and
credit cards several feet away!
 NMR Sample 5 mm NMR
sample tube

Position
(prior to release into probe) upper level
of NMR
RF energy solution

NMR sample
positioned
at top of probe

Liquid Nitrogen
-196°C (77.4 K)

Liquid Helium
-269°C (4.2 K)

Superconducting magnets
require continuous cooling.
 Interpretation of 1H-NMR Data

Chemical shifts - nonequivalent H’s give unique signals along the x-axis of the spectrum.
The small, discrete energy differences between signals are measured in  or ppm units.
• Radio frequency energies are needed to “flip” nuclei from an aligned (, lower energy
state) to an opposed (, higher energy state) orientation in an external magnetic field.
The Rf energy required is influenced by the degree of electron shielding of the nucleus.
• These data provide direct evidence of the number and kinds of hydrogens in a molecule
and indirect evidence of how carbon, nitrogen, oxygen, and other atoms are connected.

TMS reference signal

tetramethylsilane
Si(CH3)4 = 0.00 
10 9 8 7 6 5 4 3 2 1 0 
increasing deshielding
increasing shielding
• The chemical shift () of each proton is the
location at which the peak occurs on the spectra,
relative to TMS

Si

tetramethylsilane (TMS)
• TMS is used as the zero point on the chemical
shift scale.
• It is chosen for many reasons, including its
relatively strong signal, and the fact that it
produces one singlet peak due to containing all
equivalent protons (will see why later).
 Chemical Shifts

This spectrum shows 2 signals: 3.75  The chemical shift (value)

of a signal having multiple
0.95 
peaks is determined by its center.

Why do these hydrogens have The higher  value of this signal

is due to less electron density
The lower  value of this signal
is due to more electron density
different chemical shifts? shielding this hydrogen. shielding this hydrogen.
 1
H-NMR - Correlation Diagram

common Chloroform (CHCl3) = 7.26  Methylene chloride Acetone (CH3COCH3) = 2.16  TMS
singlets Benzene (C6H6) = 7.32  (CH2Cl2) = 5.30 Toluene (C6H6CH3) = 2.32   0.00  

type of
attachment Protons Attached to sp2 Carbon Protons Attached to sp3 Carbon
RCH2OR ArCH3
RCH2NR2 RCOCH3

R3CH methine
Vinyl RCH2X R2CH2 methylene
RCHO Aromatic ArH R2C=CHR X = F, Cl, Br, I RCH3 methyl
Delta
Scale
() 10 9 8 7 6 5 4 3 2 1 0
even more
deshielded shielded
deshielded due to: due to:
ring currents (from  bonds) inductive effect (through  bonds)
• Protons bonded to more highly
electronegative atoms are said to be
deshielded from the effects of the applied
magnetic field, and their peaks are found
further downfield.

40
 SPIN-SPIN COUPLING
• Spin-spin coupling is the effect of
neighboring atoms’ electronic
environments on the nuclei.

• In 1H-NMR, this phenomenon is only

observed if the neighboring atoms are
close enough to feel the effects.
(Close = Through 3 bonds or less)

• Spin-spin coupling causes the peaks to

split on the NMR spectra
• The sample is almost always in
solution, and must be dissolved in
deuterated solvent
deuterium = 2H
• Since 2H does not produce a NMR
signal, there is no intereference
from the solvent
• Protons in the molecule attached
to oxygen (in an alcohol for
example) will give a broad peak
around 4.8 ppm

44
 SPIN-SPIN COUPLING
• Peaks are split by (n+1), where n is the
number of neighboring equivalent protons.

CH3CH2OCH3 Recall TMS…

Si
SPIN-SPIN COUPLING
 SPIN-SPIN COUPLING
• The distance
between each split of
the peak is called the
“coupling constant”,
and is denoted by J
• It is dependant on the
internal forces of that
specific proton for
whose peak is split,
and reported in units
of Hertz.
 SPIN-SPIN COUPLING
• The ratios of the integrated area of each
split of a peak follow the rules of Pascal’s
triangle
1
1:1
1:2:1
1:3:3:1
1:4:6:4:1
1:5:10:10:5:1
 SPIN-SPIN COUPLING
# NEARBY SPLITTING RATIO OF PEAK
EQUIV. PATTERN HEIGHTS
PROTONS
0 singlet no splitting

1 doublet 1:1

2 triplet 1:2:1

3 quartet 1:3:3:1
 SPIN-SPIN COUPLING
• The ratios of the peak
heights can help
predict if there is
splitting or overlapping
peaks, or distinguish
splitting patterns
• Split peaks can be
further split by
unequivalent
neighboring protons.
 Interpretation of 1H-NMR
Data
Spin-spin coupling (splitting) - neighboring NMR active nuclei split each other.

 nonequivalent nuclei three bonds (or less) apart mutually interact with each
other causing their NMR signals to be split into multiple peaks.

n = # of neighbors n + 1 = # of peaks in signal

HaHb
1| |3
n n+1 pattern peak ratio
0 1 singlet (s) 1
-C 2C- —

| |
1 2 doublet (d) 1:1
2 3 triplet (t) 1:2:1
3
JHH =
3 4 quartet (q) 1:3:3:1 vicinal
4 5 pentet (p) 1:4:6:4:1 coupling
many many + 1 multiplet (m) (Hz)
1st order
splitting
patterns
 Common Splitting Patterns

singlet doublet triplet quartet pentet

1:1 1:2:1 1:3:3:1 1:4:6:4:1

ethyl isopropyl

ethyl signature: quartet / triplet septet / doublet & 1 / 6 ratio

with integration ratio of 2 / 3
 1
H-NMR H
H
H

• One peak is observed H H

for each set of equivalent

protons H H

H
H
H

• Protons are considered equivalent if they

are located in the same electronic
environment
 downfield
1
H-NMR upfield

• The integrated areas under the peaks are

directly proportional to the number of that
type of hydrogen in the molecule.
 H-NMR
1

• Examples of molecules, and equivalent

protons
O

O
O

O
N
O

30
H-NMR
1
1-bromo-2-tertbutylethane
 Summary - NMR
Spectroscopy
1. range of wavelengths - radio frequencies 10's to 100's of megahertz (MHz)
2. effect of energy absorbed - select spinning nuclei are flipped against a strong external
magnetic field
3. utility - detailed structural information, in the form of:
a. chemical shift - indication of electronic environment around nucleus (qualitative)
b. spin/spin splitting or coupling - # of neighboring nuclei (quantitative)
c. integration - relative numbers of nuclei contributing to each signal (quantitative)
4. common applications - very reliable method in structure elucidation
a. proton nuclear magnetic resonance spectroscopy (1H-NMR): provides information
on the number and kind of protons in a compound
b. carbon nuclear magnetic resonance spectroscopy (13C-NMR): provides information
on the number and kind of carbons in a compound (no integration)
c. heteroatom NMR - 15N, 17O, 19F, 31P + other nuclei
5. sample requirements - mg sample size, normally dissolved in solution
6. additional applications
a. special techniques can give spatial information - atomic distances
b. diagnostic imaging of living systems - Magnetic Resonance Imaging (MRI)
 NMR Spectroscopy Problems
• A compound has the formula C2H6O and
yields 1 peak by NMR spectroscopy.
Propose a structure.
 NMR Spectroscopy Problems
• The molecule shown below gives a singlet, a
quartet, and a triplet in 3:2:3 ratio. At what ppm
do these peaks show up as?

.
O
CH3 C CH2CH3

.
 H NMR of 5-methyl 2-furfural
1

O
H3C

H
THANK YOU