Espectroscopia de Ressonância

Magnética Nuclear
 Modern Spectroscopic Methods
• Revolutionized the study of Organic Chemistry

• Determine the exact structure of small to medium

size molecules in a few minutes.
 Relações entre Comprimento de
onda e Espectroscopia
Região Espectral Energia do fóton Molecular Energy
Changes

UV-Visível ~ 100 kcal/mol Eletrônica

Infravermelho (IV) ~ 10 kcal/mol Vibrações das

ligações
Rádio < 0,1 kcal/mol Estados de spin
nuclear em um
campo magnético
 The Great Radio Controversy

Who Invented Radio?

•Tesla coil, 1891
•Remote-controlled boat, 1898
•US patents for fundamental
radio technologies, 1900

Nikola
Tesla?
http://www.pbs.org/tesla/ll/ll_whoradio.html
The Tesla Coil
 Tesla’s vision for wireless communication

Wall Street financier Promotional illustration for Tesla's tower

J. P. Morgan Tesla's "World System" with dome frame.
Completed in 1904.
 Spin dos Núcleos Atômicos
• Átomos de Spin 1/2 : número de massa é ímpar.
exemplos: 1H e 13C.

• Átomos de Spin 1: número de massa é par.

exemplos: 2H e 14N.

• Átomos de Spin 0: número de massa é par.

exemplos: 12C e 16O.
 Spin Quantum Numbers of Some Nuclei
The most abundant isotopes of C and O do not have spin.

Element 1H 2H 12C 13C 14N 16O 17O 19F

Nuclear Spin
Quantum No 1/2 1 0 1/2 1 0 5/2 1/2
(I)
No. of Spin 2 3 0 2 3 0 6 2
States

Elements with either odd mass or odd atomic number

have the property of nuclear “spin”.

The number of spin states is 2I + 1,

where I is the spin quantum number.
Estados de Energia de Prótons Submetidos a
um Campo Magnético Externo

∆ E = λ a b so rb e d lig h t

A p p lie d

M a g n e tic

F ie ld

H
ext
 Nuclear Spin Energy Levels
N

-1/2

In a strong magnetic
unaligned
field (Bo) the two
spin states differ in
energy.

+1/2
aligned
Bo S
 Ressonância Magnética Nuclear (RMN)
Nuclear Magnetic Resonance (NMR)

• Ressonância – fótons de ondas de rádio podem

apresentar a diferença de energia exata entre os
estados de spin + ½ and – ½ resultando na
absorção de fótons enquanto os prótons têm seus
estados de spin alterados.

• Magnética – um campo magnético forte causa

uma pequena diferença de energia entre os estados
de spin + ½ e – ½.

• Nuclear – nuclídeos de spin ½ (e.g. prótons)

comportam-se como pequenas barras magnéticas.
 Nuclear Resonance

absorption of energy by the

spinning nucleus
 The Larmor Equation!!!
∆E = kBo = hν can be transformed into

gyromagnetic
ratio γ
frequency of γBγ0
the incoming
νν == Bo
radiation that
will cause a 2π
π
2π
transition strength of the
magnetic field

γ is a constant which is different for

each atomic nucleus (H, C, N, etc)
 Resonance Frequencies of Selected Nuclei
Isotope Abundance Bo (Tesla) Frequency(MHz) γ(radians/Tesla)
1H 99.98% 1.00 42.6 267.53
1.41 60.0
2.35 100.0
7.05 300.0

13C 1.108% 1.00 10.7 67.28

2.35 25.0
7.05 75.0
 The NMR Experiment
• The sample, dissolved in a suitable NMR solvent
(e.g. CDCl3 or CCl4) is placed in the strong
magnetic field of the NMR.

• The sample is bombarded with a series of radio

frequency (Rf) pulses and absorption of the radio
waves is monitored.

• The data is collected and manipulated on a

computer to obtain an NMR spectrum.
The NMR Spectrometer
The Energy Separation Depends on Bo

- 1/2

∆E = kBo = hν
degenerate
at Bo = 0

+ 1/2

Bo
increasing magnetic field strength
Classical Instrumentation:
The Continuous-Wave NMR

typical before 1965;

field is scanned
 A Simplified 60 MHz
NMR Spectrometer
RF (60 MHz) hν
Oscillator absorption RF
Recorder
signal Detector
Transmitter
Receiver

MAGNET MAGNET
~ 1.41 Tesla
N S (+/-) a few ppm

Probe
 Modern Instrumentation:
the Fourier-Transform NMR

FT-NMR
requires a computer
 PULSED EXCITATION
N

ν2
ν1
O
BROADBAND
RF PULSE CH2 C CH3
contains a range
of frequencies ν3
(ν1 ..... νn)

S
All types of hydrogen are excited
simultaneously with the single RF pulse.
 Some Generalizations
• NMR solvents contain deuterium
• Tetramethylsilane (TMS) is the
reference.
• Chemical shift in Hz from TMS vary
according to frequency of
spectrometer!
δ) are independent of
• Delta values (δ
frequency of spectrometer (ppm).
Espectro de RMN de Hidrogênio
(Proton NMR Spectrum)
 The NMR Spectrum
• The vertical axis shows the intensity of Rf
absorption.
• The horizontal axis shows relative energy at
which the absorption occurs (in units of parts per
million = ppm)
• Tetramethylsilane (TMS) in included as a standard
zero point reference (0.00 ppm)
• The area under any peak corresponds to the
number of hydrogens represented by that peak.
NMR Spectrum of Phenylacetone

O
CH2 C CH3

EACH DIFFERENT TYPE OF PROTON COMES AT A DIFFERENT

PLACE - YOU CAN TELL HOW MANY DIFFERENT TYPES OF
PROTONS THERE ARE BY INTEGRATION.
O Deslocamento Químico
(The Chemical Shift)
PEAKS ARE MEASURED RELATIVE TO TMS
Rather than measure the exact resonance position of a
peak, we measure how far downfield it is shifted from TMS.

CH3 reference compound

tetramethylsilane
CH3 Si CH3 “TMS”
CH3
Highly shielded
protons appear
way upfield.

TMS Chemists originally

shift in Hz thought no other
compound would
downfield
come at a higher
n 0 field than TMS.
HIGHER FREQUENCIES GIVE LARGER SHIFTS

The shift observed for a given proton

in Hz also depends on the frequency
of the instrument used.
Higher frequencies
= larger shifts in Hz.

TMS
shift in Hz
downfield
n 0
 THE CHEMICAL SHIFT
The shifts from TMS in Hz are bigger in higher field
instruments (300 MHz, 500 MHz) than they are in the
lower field instruments (100 MHz, 60 MHz).
We can adjust the shift to a field-independent value,
the “chemical shift” in the following way:
parts per
million

chemical shift in Hz
shift
= δ = = ppm
spectrometer frequency in MHz

This division gives a number independent

of the instrument used.

A particular proton in a given molecule will always come

at the same chemical shift (constant value).
 Chemical Shift (δδ)
• The chemical shift (δ
δ) in units of ppm is defined as:

δ = distance from TMS (in hz)

radio frequency (in Mhz)

• A standard notation is used to summarize NMR

spectral data. For example p-xylene:
δ 2.3 (6H, singlet)
δ 7.0 (4H, singlet)

• Hydrogens in identical chemical environments

(equivalent hydrogens) have identical chemical shifts.
PROTONS DIFFER IN THEIR SHIELDING
All different types of protons in a molecule
have a different amounts of shielding.

They all respond differently to the applied magnetic

field and appear at different places in the spectrum.

This is why an NMR spectrum contains useful information

(different types of protons appear in predictable places).

SPECTRUM
DOWNFIELD UPFIELD
Less shielded protons Highly shielded
appear here. protons appear here.
It takes a higher field
to cause resonance.
 Overview of where protons
appear in an NMR spectrum

C-H where C is
CH on C
attached to an
acid aldehyde benzene alkene next to aliphatic
COOH CHO CH =C-H electronega- pi bonds C-H
tive atom
X=C-C-H
X-C-H
12 10 9 7 6 4 3 2 0
 Some Specific Structural Effects on
NMR Chemical Shift
Type of Hydrogen δ (ppm
Alkyl (C – H) 0.8 – 1.7

Alkyl Halide (RCH2X) 3-4

Alkene (R2C=CH2) 4-6

Aromatic (e.g. benzene) 6-8

Carboxylic Acid (RCOOH) 10 - 12

 Shielding – The Reason for
Chemical Shift Differences
• Circulation of electrons within molecular
orbitals results in local magnetic fields that
oppose the applied magnetic field.

• The greater this “shielding” effect, the

greater the applied field needed to achieve
resonance, and the further to the right
(“upfield”) the NMR signal.
 Structure Effects on Shielding
• Electron donating groups increase the
electron density around nearby hydrogen
atoms resulting in increased shielding,
shifting peaks to the right.

• Electron withdrawing groups decrease the

electron density around nearby hydrogen
atoms resulting in decreased shielding,
(deshielding) shifting peaks to the left.
DESHIELDING AND ANISOTROPY
Three major factors account for the resonance
positions (on the ppm scale) of most protons.

1. Deshielding by electronegative elements.

2. Anisotropic fields usually due to pi-bonded

electrons in the molecule.
3. Deshielding due to hydrogen bonding.
 Generalizations
• electrons shield nucleus
• electronegativity: withdraws electrons to
deshield nucleus
• downfield (deshielding) = left side of
spectrum
• upfield (shielding) = right side of
spectrum
• delta values increase from right to left!
 DESHIELDING BY
ELECTRONEGATIVE ELEMENTS
DESHIELDING BY AN ELECTRONEGATIVE ELEMENT

δ- δ+ Chlorine “deshields” the proton,

Cl C H that is, it takes valence electron
density away from carbon, which
δ- δ+ in turn takes more density from
electronegative hydrogen deshielding the proton.
element

NMR CHART

“deshielded“ highly shielded

protons appear protons appear
at low field at high field

deshielding moves proton

resonance to lower field
Electronegativity Dependence
of Chemical Shift
Dependence of the Chemical Shift of CH3X on the Element X

Compound CH3X CH3F CH3OH CH3Cl CH3Br CH3I CH4 (CH3)4Si

Element X F O Cl Br I H Si
Electronegativity of X 4.0 3.5 3.1 2.8 2.5 2.1 1.8
Chemical shift δ 4.26 3.40 3.05 2.68 2.16 0.23 0

most TMS
deshielded
deshielding increases with the
electronegativity of atom X
 Substitution Effects on
Chemical Shift
most The effect
deshielded increases with
CHCl3 CH2Cl2 CH3Cl
greater numbers
7.27 5.30 3.05 ppm of electronegative
atoms.

most
deshielded -CH2-Br -CH2-CH2Br -CH2-CH2CH2Br
3.30 1.69 1.25 ppm

The effect decreases

with incresing distance.
 ANISOTROPIC FIELDS
DUE TO THE PRESENCE OF PI BONDS

The presence of a nearby π bond

greatly affects the chemical shift.

Benzene rings have the greatest effect.

 Ring Current in Benzene

Circulating π electrons

Deshielded
H H fields add together

Bo Secondary magnetic field

generated by circulating π
electrons deshields aromatic
protons
ANISOTROPIC FIELD IN AN ALKENE

protons are
deshielded
Deshielded

fields add
H H shifted
downfield

C=C
H H
secondary
magnetic
(anisotropic)
field lines
Bo
ANISOTROPIC FIELD FOR AN ALKYNE

H
C
C
H secondary
magnetic
(anisotropic)
Shielded hydrogens field
Bo
are shielded
fields subtract
HYDROGEN BONDING
HYDROGEN BONDING DESHIELDS PROTONS

The chemical shift depends

R on how much hydrogen bonding
is taking place.
O H H
Alcohols vary in chemical shift
O H O R from 0.5 ppm (free OH) to about
5.0 ppm (lots of H bonding).
R

Hydrogen bonding lengthens the

O-H bond and reduces the valence
electron density around the proton
- it is deshielded and shifted
downfield in the NMR spectrum.
SOME MORE EXTREME EXAMPLES

O H O Carboxylic acids have strong

R C C R hydrogen bonding - they
form dimers.
O H O

With carboxylic acids the O-H

absorptions are found between
10 and 12 ppm very far downfield.
H3C O
O
H
In methyl salicylate, which has strong
O internal hydrogen bonding, the NMR
absortion for O-H is at about 14 ppm,
way, way downfield.

Notice that a 6-membered ring is formed.

 NMR Correlation Chart
-OH -NH
DOWNFIELD UPFIELD
DESHIELDED SHIELDED
CHCl3 , H

TMS

12 11 10 9 8 7 6 5 4 3 2 1 0 δ (ppm)
H
CH2F CH2Ar C-CH-C
RCOOH RCHO C=C CH2Cl CH2NR2
CH2S C
CH2Br
CH2I C C-H C-CH2-C
CH2O C=C-CH2 C-CH3
CH2NO2 CH2-C-
O
 Spin-Spin Splitting
• Non-equivalent hydrogens will almost always
have different chemical shifts.

• When non-equivalent hydrogens are on adjacent

carbon atoms spin-spin splitting will occur due to
the hydrogens on one carbon feeling the magnetic
field from hydrogens on the adjacent carbon.

• The magnitude of the splitting between two

hydrogens (measured in Hz) is the coupling
constant, J.
 Pascal’s Triangle
Pattern Relative Peak Height

Singlet 1
Doublet 1:1
Triplet 1:2:1
Quartet 1:3:3:1
Quintet 1 :4 : 6 : 4 : 1
 The n + 1 Rule
If Ha is a set of equivalent hydrogens and Hx is an
adjacent set of equivalent hydrogens which are not
equivalent to Ha:

• The NMR signal of Ha will be split into n+1 peaks by

Hx (where n = number of hydrogens in the Hx set).

• The NMR signal of Hx will be split into n+1 peaks by

Ha (where n = number of hydrogens in the Ha set).
 NMR: Some Specific Functional
Group Characteristics
• O-H and N-H will often show broad peaks
with no resolved splitting, and the chemical
shift can vary greatly.

• Aldehyde C-H is strongly deshielded.

(δ = 9-10 ppm)

• Carboxylic Acid O-H is very strongly

deshielded. (δ = 10-12 ppm)
 NMR: Some Specific Functional
Group Characteristics
• Ortho splitting on aromatic rings is often
resolved, but meta and para splitting is not.

• Cis and trans H’s on alkenes usually show

strong coupling, but vicinal H’s on alkenes
show little or no resolved coupling.
13.8 Integration
 INTEGRATION OF A PEAK
Not only does each different type of hydrogen give a
distinct peak in the NMR spectrum, but we can also tell
the relative numbers of each type of hydrogen by a
process called integration.

Integration = determination of the area

under a peak

The area under a peak is proportional

to the number of protons that
generate the peak.
 Benzyl Acetate
The integral line rises an amount proportional to the number of H in each peak

METHOD 1
integral line

integral
line

simplest ratio
55 : 22 : 33 = 5:2:3 of the heights
 Benzyl Acetate (FT-NMR)
Actually : 5 2 3

58.117 / 11.3 21.215 / 11.3 33.929 / 11.3

= 5.14 = 1.90 = 3.00

O
CH2 O C CH3

METHOD 2
digital assume CH3
33.929 / 3 = 11.3 per H
integration

Integrals are
good to about
10% accuracy.

Modern instruments report the integral as a number.

 Unknown A
(Figure 9.20 Solomons 7th ed.)
• Formula: C3H7I

• IHD = 0

• No IR data provided

• 1HNMR δ: 1.90 (d, 6H), 4.33 (sept., 1H)

 Unknown B
(Figure 9.20 Solomons 7th ed.)
• Formula C2H4Cl2

• IHD = 0

• No IR data given

• 1HNMR δ: 2.03 (d, 3H), 4.32 (quartet, 1H)

 Unknown C
(Figure 9.20 Solomons 7th ed.)
• Formula: C3H6Cl2

• IHD = 0

• No IR data given

• 1HNMR δ: 2.20 (pent., 2H), 3.62 (t, 4H)

 Unknown A
(Figure 14.27 Solomons 7th ed.)
• Formula = C9H12

• IHD = 4

• No IR data given

• 1HNMR δ: 1.26 (d, 6H), 2.90 (sept., 1H),

7.1-7.5 (m, 5H)
 Unknown B
(Figure 14.27 Solomons 7th ed.)
• Formula = C8H11N

• IHD = 4

• IR shows two medium peaks between 3300 and

3500 cm-1

• 1HNMR δ: 1.4 (d, 3H), 1.7 (s, br, 2H),

4.1(quart., 1H), 7.2-7.4 (m, 5H)
 Unknown C
(Figure 14.27 Solomons 7th ed.)
• Formula = C9 H10

• IHD = 5

• No IR data given

• 1H NMR δ: 2.05 (pent., 2H),

2.90 (trip., 4H), 7.1-7.3 (m, 4H)
 Unknown H
(Figure 9.48 Solomons 7th ed.)
• Formula = C3H4Br2

• IHD = 1

• No IR data given

• 1HNMR δ: 4.20 (2H), 5.63 (1H), 6.03 (1H)

 Unknown Y
(Figure 14.34 Solomons 7th ed.)
• Formula = C9H12O

• IHD = 4

• IR shows a strong, broad, absorbance centered at

3400 cm-1

• 1HNMR δ: 0.85 (t, 3H), 1.75 (m, 2H),

4.38 (s, br, 1H), 4.52 (t, 1H),
7.2-7.4 (m, 5H)