CHAPTER 10

Spectroscopy:
Nuclear Magnetic Resonance
 Fundamentals of Spectroscopy
Spectroscopy is the interaction of light with molecules. Since light can be
easily “watched,” we can observe how it is absorbed, reflected and diffracted by
an unknown molecule. Since the structure of the molecule is the primary
determinant of how light interacts with the molecule, we can determine the
structure of an unknown molecule by shining light on the molecule and
“watching” what happens.

In general, light “interacts” with a molecule in the “ground state” by giving the
molecule energy in the form of light and exciting the molecule into an “excited
state” meaning high energy state. The difference in energy between the ground
and excited state depends on molecular structure and is the basis for
spectroscopic structure determination.

Excited State

Energy This energy difference depends on the

!E = h" structural features of the molecule.

Ground State
 Types of light that “excite” molecules.
Electromagnetic radiation can be described as a wave
having a wavelength (λ), a frequency (ν) and a velocity (c).

ΔE=hν

Type of Light Wavelength Energy Transition

X-rays <50 nm >300 kcal/mol Core Electrons

Extreme Ultraviolet 50-200 nm 40-300 Kcal/mol Valence Electrons

Ultraviolet 200-400 nm
Visible 400-800nm

Near Infrared 1-20 um 2-35 kcal/mole Vibrations

Far Infrared 20-1000 um 0.1-2 kcal/mole Vibrations

Microwave 1-100 mm 10-4 kcal/mol Rotations

Radiowave (NMR) 0.1-1 M 10-6 kcal/mol Nuclear-spin
 Types of Spectroscopy
Spectroscopy is a technique for analyzing the structure of molecules, usually
based on how they absorb electromagnetic radiation. Four types are most often
used in organic chemistry:
Nuclear Magnetic Resonance spectroscopy (NMR)
Infrared spectroscopy (IR)
Ultraviolet spectroscopy (UV)
Mass spectroscopy (MS)

How to they identify a unknown molecule?

NMR: structure and connectivity of carbon-hydrogen framework

IR: functional group identification
UV: conjugation of π - system
MS: molecular weight and formula

A combination of these techniques are used to identify the structure

of a molecule.
 Structure Identification

H2SO4
or or
OH

MW = 136 MW = 118

MS: What is molecular weight? (MW = 118)

IR: Functional groups?
-OH present? NO
-double bond? YES
UV: Is it conjugated (next to) to the phenyl group? YES
NMR: What is carbon-hydrogen framework like?
Is the double bond cis or trans? trans
Nuclear Magnetic Spectroscopy (NMR)
Some nuclei possess spin and this property is exploited in NMR
Spectroscopy. Only those nuclei possessing spin can be detected by this
method. We will focus on the NMR of 13C and 1H, but many other nuclei
can be studies by NMR.
What is “spin”? Consider the 1H nucleus which is positively charged and rotating
along some axis. In the presence of a powerful magnetic field, the nucleus wants to
align with the field. Some want to align parallel (α) and some anti-parallel (β) to
the magnetic field.

+ Magnetic moment

Axis of rotation

! "
 Resonance
The α and β spin states have different energies in the magnetic field.
α-spin nuclei are lower in energy than β-spin nuclei and, as predicted by the Boltzman
equation, the lower energy state is more populated. Upon excitation with
electromagnetic radiation, the α-state can be converted to the β-state and this results
in nuclear magnetic resonance which in turn gives rise to a signal in the spectra.

! anti-parallel
I = -1/2 Resonance occurs when the nuclei
h# are irradiated with the proper
E
frequency to cause a spin flip.
" parallel
I = +1/2
radio frequency

!-spin

The difference in energy between

Energy

the α and β states depends Electromagnetic

Radiation
directly on the external magnetic
field strength, H0.

"-spin

0
B0 (Magnetic Field Strength)
 More Facts about Resonance
The difference in energy between the α and β
states depends directly on the external magnetic
field strength, H0.
21,150 G 90 MHz
42,300 G 180 MHz

70,500 G 300 MHz

The energy difference is very small. Consequently the α-state is only slightly more populated than
the β-state. This results in NMR being a relatively insensitive technique. For example, if
1,000,000 hydrogens are placed in a magnetic field with a strength of 14,100 Gauss (60 MHz),
500,010 will be in the lower spin state and 499,990 will be in the higher spin state. Thus out the
1,000,000 hydrogens only 10 are available for excitation to the higher state.

Higher fields afford higher sensitivity. The energy difference between the two states (and also
the population difference between them) is dependent upon the magnetic field. Higher field = greater
energy difference = lower energy level more populated = more sensitivity.

NMR active nuclei resonate at different frequencies. For example, when using a 11.74 Tesla
magnet, a hydrogen nuclei resonates at 500 MHz, and a carbon nuclei at 125 MHz. Spectrometers are
referred to by the frequency at which a hydrogen nuclei would resonate if placed in the instrument.

In comparison with other techniques, NMR is slow. In practice what this means is that the
spectrum that is obtained represents an average of all of conformations and orientations which are
present in equilibrium at that temperature. Detecting distinct conformers (e.g., two interconverting
chair conformations) requires special experimental conditions.
NMR Spectroscopy Facilities at OSU

Solution:
• 250 MHz
• 400 MHz (2)
• 500 MHz
• 600 MHz (2)
• 800 MHz

Solid State:
• 300 MHz (2)
• 400 MHz (2)
Many nuclei undergo magnetic resonance.

In general, nuclei composed of an odd number of protons (1H and its

isotopes, 14N 19F, and 31P) or an odd number of neutrons (13 C) show
magnetic behavior.
If both the proton and neutron counts are even (12C or 16O) the nuclei
are non-magnetic.
 An NMR Experiment
There are two ways in which an NMR Experiment can be conducted.

Fixed Magnetic Field Strength / Vary Rf
1. Place the protons in a magnetic field.
2. Apply a radio frequency (Rf) until an absorption is noted.
3. Record the radio frequency needed for absorption to be
observed.
Fixed Radio Frequency/Vary Magnetic Field Strength
1. Place the protons in a magnetic field.
2. Apply a set radio frequency (Rf)
3. Vary magnetic field strength (H0) until absorption is observed.

Absorbance Absorbance

Fixed Field Strength Fixed Radio Frequency

H0 = 21,500 Gauss Rf = 90 MHz

Rf Rf
90 MHz
21,500 Gauss
Vary Rf Vary H0
 Shielding
The chemical shift of a particular hydrogen depends upon the electron density that
surrounds it. The motion of the electrons creates a magnetic field which acts in opposition to the
external magnetic field. Thus the electrons “shield” the nucleus from the applied magnetic field. The
degree of shielding determines where in the spectra the resonance for a particular hydrogen will
appear. Hydrogens can be described as shielded or deshielded relative to each other.

C H e- cloud
Heff = Ho - Hinduced

H0 HInduced

The degree of shielding of a nucleus

depends upon its surrounding electron
density.
Adding electrons increases shielding.
Removing electrons causes deshielding.
 The NMR Spectrum and Chemical Shift
NMR Spectra are usually recorded by reporting the position of peaks relative to a standard compound.
Tetramethylsilane TMS is usually the standard. It’s protons are shielded relative to most protons due
to the low electronegativity of silicon. A given proton will undergo resonance at a field strength that
differs from that of the standard (TMS). This difference is known as the chemical shift.

Chemical shifts (d) are measured in ppm and always

given relative to standard. They are defined by the
following formula:

= (i–s)/o x 106 ppm

where i = frequency of the hydrogen of interest (in Hz)

Downfield s = frequency of the standard (in Hz)
Upfield o = operating frequency of the magnet (in Hz)

10 ppm 0

Chemical shift values are independent of the

field strength of the magnet.
Tetramethylsilane (TMS, (CH3)4Si) is the most
common internal standard, and is assigned a
chemical shift of 0.00 ppm.
!s !s

!1 !1
100 Hz 200 Hz

1 ppm 1 ppm
100 MHz Spectrum 200 MHz Spectrum
 Upfield and Downfield?
Lets irradiate a proton with 180 MHz exactly. The change of α−β energy
states requires 42,276 gauss at the proton.
Due to shielding, the applied field must be somewhat higher than 42,276
gauss to allow the effective field to have the resonance value of 42,276
gauss. So more shielding means higher field necessary for
resonance.

TMS
Low field (downfield) High field (upfield)
High Rf frequency Low Rf frequency

10 0

increasing field

increasing Rf frequency
 Effect of Shielding on Chemical Shift.
Shielding causes a displacement of an NMR peak to the right in the
spectrum (shifted upfield).
Deshielding causes a displacement to the left (shifted downfield).

CH3 TMS
Cl-CH2-O-CH3
Rf = 90 MHz
δ(CH3) = 340 x 106/ 90 x 106 = 3.77
340 Hz
CH2 δ(CH2) = 500 x 106 / 90 x106 = 5.55
500 Hz

downfield H0 upfield
Multiple substituents exert a cumulative effect.

The deshielding
influence of electron
withdrawing groups
diminishes rapidly with
distance.
 The NMR Spectrum and Chemical Shift
NMR Spectra are usually recorded by reporting the position of peaks relative to a standard compound.
Tetramethylsilane TMS is usually the standard. It’s protons are shielded relative to most protons due
to the low electronegativity of silicon. A given proton will undergo resonance at a field strength that
differs from that of the standard (TMS). This difference is known as the chemical shift.

Chemical shifts (d) are measured in ppm and always

given relative to standard. They are defined by the
following formula:

= (i–s)/o x 106 ppm

where i = frequency of the hydrogen of interest (in Hz)

Downfield s = frequency of the standard (in Hz)
Upfield o = operating frequency of the magnet (in Hz)

10 ppm 0

Chemical shift values are independent of the

field strength of the magnet.
Tetramethylsilane (TMS, (CH3)4Si) is the most
common internal standard, and is assigned a
chemical shift of 0.00 ppm.
!s !s

!1 !1
100 Hz 200 Hz

1 ppm 1 ppm
100 MHz Spectrum 200 MHz Spectrum
1H Chemical Shifts-Electronegativity
CH3-A A Electronegativity Chemical Shift (δ)

CH3-Li Li 1.0 -1.0

CH3-SiMe3 SiMe3 1.7 0.0

CH3-H H 2.1 0.2
CH3-CH3 CH3 2.5 0.9
CH3-NH2 NH2 3.1 2.3
CH3-OH OH 3.5 3.4
CH3-F F 4.0 4.2

CH3-Cl Cl 3.2 3.1

CH3-Br Br 3.0 2.7

CH3-I I 2.7 2.2

 Field Anisotropy
The deshielding influence of electron withdrawing groups diminishes
rapidly
R CH3 with distance.
1.1 ppm

H2C CH2 5 ppm

• Increasing s character in bond more
electronegative carbon.
H 3 ppm • What about acetylene and benzene?

7 ppm

Magnetic field is stronger near the Magnetic field is weaker near the
protons-->deshielded protons-->shielded

Hinduced H

electron
Ho Hinduced movement
H

Induced magnetic field

Electrons are delocalized and can move around the ring, creating a
ring current and induced field.
 Resonance Effects
Electron Withdrawing Groups

O O
Ha Ha Ha
Hb Hb Hb

! Ha = 5.7 ! Ha = 6.0
! Hb = 5.7 ! Hb = 7.0

Electron Donating Groups

Ha Ha Ha
Hb X X
! Ha = 5.7
! Hb = 5.7

Ha Ha Ha

OCH3 NMe2 OLi

! Ha = 5.4 ! Ha = 4.8 ! Ha = 4.3

 Magnetic Equivalence
Chemically equivalent protons are magnetically equivalent and,
therefore, have the same chemical shift.

Chemically inequivalent protons are usually magnetically

inequivalent and have different chemical shifts.

Ha Hb
R Ha R
R C Hb Chemically
equivalent
Hc R Hb R Ha

R Ha Hb
Chemically
inequivalent

Hb R Ha
Conformational interconversion may result in
equivalence on the NMR time scale.
In the case of the rapid rotation of the methyl group in
chloroethane, or the rapid conformation flip in cyclohexane, the
observed chemical shifts are the averages of the values that
would be observed without the rapid rotation or flip.