Nuclear Magnetic

Resonance Spectroscopy

Part Two: More Advanced

Considerations (I)

1
 The Mechanism of Coupling:
Coupling Constant

Spin of nucleus and Spin of nucleus and

electron paired or electron parallel
opposed (lower energy) (higher energy)

Figure 1. Dirac vector model for nucleus

and electron spins

2
 C−H

․
(a) (b)
Figure 2. (a) The most stable arrangement when
both nuclei have spin (b) Typical C-H bond: only
the H nucleus has spin

3
The magnitude of the spin interaction based on the
Dihedral angle between adjacent CH bonds.

H H
C1 C2

α α
Ha
Ha Hb
C2 Hb
C1

Side view End view

Figure 3. Definition of the dihedral angle α

4
 HH

14
12 H

J (Hz) 10 H H
8
6
H
4
2
0° 30° 60° 90° 120° 150° 180°
α
Figure 4. Variation of the coupling constant J
with the dihedral angle

5
 Ha Ha

Hb
Hb

Jaa = 10 – 14 Hz Jae = 4 – 5 Hz
α = 180° α = 60°

Notice: Jee = 4 – 5 Hz (α = 60°)

6
 Hb
Ha Ha

Hb

J = 10 ~ 12 Hz J = 7 ~ 8 Hz
α = 0o α = 120o

Notice: Jcis > Jtrans

7
2. Magnetic Equivalence

In CH3I: all three protons are magnetically

Equivalent, no spin-spin splitting observed.

a.Identical magnetic environment with same

chemical shift.
b. All the protons couple to all other protons in
the same molecule by the same J values.

8
 H H H H
C1 C2 C1
Vicinal protons Geminal proton
(neighbor) (twin)

e.g. esp in cycloalkane derivatives,

Two geminal Hs are not magnetically equvalent.

9
 Br
Ha

Cl CH3

Hb
CH3

J gem ~ 5 Hz

Ha is perturbed more by Cl than Hb

Ha & Hb have different chemical shift.

10
 CH3I singlet D−CH2−I

Deuterium part Proton part

(not observed in 60
MHz NMR), observed
at 9.22 MHz

Figure 5. A comparison of the spectra of MeI and DCH2I

11
From Experiment:
JHH = 6.55 x JHD

JHH / JHD = µH / µD = 6.55

Ratio of magnetic moment of the two nuclei

(see p.85 Table: 42.6/6.5 ~ 6.55)

12
Don’t confuse spin-spin splitting with coupling

Coupling is necessary, but not sufficient, for

spin-spin splitting to occur.

I
Ha Hb

H & D : spin-spin splitting

Ha & Hb: chemically and magnetically equivalen
J HaD & J HbD are equivalent
13
 Deuterium part Proton part

CH2: D:

+1 -1 +1 0 -1
0

14
 C
• C1

H H H H

Figure 6. The mechanism of geminal coupling

15
 4
0

3
J gem 0

2
0

190° 100° 110° 120° 130°

0
Figure 7. The dependenceα of the magnitude of
the J gem on the HCH angle α.
0

16
 H
H
H
H H
H

JHH ≅ 12 – 18 Hz JHH ≅ 0 – 3 Hz JHH ≅ 5 Hz

α ≅ 109° α ≅ 120° α ≅ 118°

Figure 8. Some typical values of geminal coupling constants

17
3. Failure of the n+1 rule due to magnetic
non-equivalence within a group

e.g. Germinal protons have spin-spin splitting.

(b) (c)
H H
H (d)
(a)

Styrene oxide

18
19
20
Chemical equivalence:
protons attached to the same carbon may be
Identical with respect to chemical reactions

Magnetic non-equivalence:
These protons may have different magnetic
Environment and chemical shifts.

21
4. Alkenes

Diamagnetic Anisotropy of
πelectrons
Chemical shifts, δ:
Protons at sp2 > protons at sp3
Ha Hb

R Hc

In general: δ Ha ≠ δ Hb ≠ δ Hc
Jab ≠ Jac ≠ Jbc
22
Ha Hb Ha Hb

Hc Hc

cis trans geminal

J ≅ 6 ~ 15 Hz J ≅ 11 ~ 18 Hz J ≅ 0 ~ 1005 Hz

23
24
25
5. Mechanism of Coupling in Alkenes;
allylic Coupling

Ha

Ha C1 Hb C1 Hb

J ~ 0 – 3 Hz J ~ 0 – 3 Hz

Allylic Coupling

26
 Mechanism:
π-δInteractions in allylic (CH=C-CH) and
homo-allylic (CH-C=C-CH) couplings

Hb
Ha C3 C2
C1 Ha Hb
C3 C2 C1

Maximum interaction Minimum interaction

Figure 16. The geometry of allylic coupling

27
Example Models of Allylic splitting:

H H
Cl H Ha H
H3C H H3C Cl C SO2
H2
1 2 3

28
 H H

(3)
C SO2
H2

A graphical Analysis of NMR Spectrum of

Compound 3.

29
 * Long-Range HH Couplings

• The meta (4J) coupling in aromatics

ca. + 2 ~ 3 Hz, in contrast to the 4J allylic coupling;
2. it is largest (1 ~ 2 Hz) in a planar zig-zag orientation,
i.e. ex-ex coupling in cyclohexanes
exo-exo couplings in camphane

H H
H H
H
H
1 ~ 1.5 Hz 7 ~ 8 Hz
1 ~ 2 Hz
30
 In aromatic system:
A methyl (or CH2X) couples to the ortho-proton
also considered a π-δinteraction.

Aromatic ring is less double character than

a normal olefin
coupling is smaller (0.5 ~ 1.5 Hz)
X

H H
H

31
 6. Protons on Oxygen: Alcohols

-CH-OH:
may show spin-spin splitting (like geminal coupling)
or no coupling observed.

Factors:  affect rate of exchange of

hydroxyl protons
7.Temperature
8.Purity of the sample
9.The solvent used
32
Rapid chemical exchange decoupled spin interaction

In general:
1. NMR transitional event about 10-2 ~ 10-3 sec.
2. Intermolecular proton of OH exchange
about 105 proton/sec:
Means residence time only 10-5 sec before
it exchange
R-OHa + R’-OHb <=> R-OHb + R’-OHa

Thus make OH and other proton decoupled.

33
Ethanol at r.t.: OH shows singlet.
If purifies to eliminate impurities
(esp. trace of water or acid), thus slowing
the proton exchange rate, OH-CH2 coupling can
be observed.
OH CH2 CH3
JCH2OH
JCH2OH JCH2CH3
JCH2CH3

5.28δ 3.62δ 1.17δ 34

7. Acid/Water and Alcohol/Water Mixtures

OH (acid) CH3
CH3COOH

OH (water)
H-OH

OH (mixture) CH3
1:1 mixture

35
 Only two peaks are seen in mixtures of
acetic acid/ water

CH3COOHa + H-OHb ⇔ CH3COOHb + H-OHa

• OH (mixture) δ depends on the ratio of the mixtu

• Rapid proton exchange leads to peak broadening

36
 SLOW
nmr sees both
Types of protons

Increasing INTERMEDIATE
rate of Transitional spectra
exchange

VERY RAPID
nmr sees average
Environment only

Figure 23. The effect of rate of exchange on the NMR spectrum of a

Hydroxylic compound dissolved in water 37
 8. Proton on Nitrogen: Amines

Intermolecular proton exchange fast enough to

decouple spin-spin interactions between protons
on nitrogen and those on the α carbon atom.

H on the α carbon also unsplit by amine H

Under strong acidic conditions, the rate of exchang

is slowed down and one can see spin-spin coupling

R-CH2-NH2 + H+ R-CH2-NH3+

38
Amides
Less basic, rate of proton exchange is slow and
coupling is often observed.

O H H H
R N H C1 N
H
H
JHH ~ 7 Hz

39
The complication of amines or amides
14
N: I =1
spin states: +1, 0, -1

H H N
N H C1 N C2 C1

Direct coupling Geminal Vicinal coupling

J ~ 50 Hz coupling
J ~ negligible

40
 NMR spectrum of CH3NH3+ in H2O (pH < 1)

J ~ 50 Hz (JNH) NH3+
H 2O CH3

J ~ 5 Hz (JNH-CH)
Intensities 1:3:3:1

41
9. Protons on Nitrogen: Quadrapole
Broadening and Decoupling

N-H coupling in NH resonance usually be

decoupled or broadened by electric quadrupole
moment of nitrogen.

quadrupole moment (QM):

I = 0 or I = ½, QM negligible
I > ½, shows large QM

42
 Prolate Oblate
Spherical
Spinning Ecllipsoidal spinning
nucleus nucleus
(I = 0 or I = ½) (I > ½) have QM

Figure 28. A comparison of the shapes of nuclei with

and without quadrupole moment

43
 -3/2
-1/2 -1/2
Br
H
+1/2 +1/2

+3/2
Rate: 102 ~ 103
per sec (slow)
Ho
Transitions rapid The proton sees only the
>> 103 per sec average and thus
decoupled from Br, which
it “believes” has only
one spin state.

Figure 29. Decoupling of a proton by rapid spin transitions

within a bromine atom
44
 Proton resonance pattern

Case 1
Spin-spin
splitting

Case 2
Nuclear
quadrupole
broadening

Case 3
Decoupling
of JNH

gure 30. The dependence of quadrupole broadening in an NH absorption

eak on nitrogen’s nuclear spin state
45
10. Amides

Quadrupole broadening at H-attached to N.

Groups attached to an amide nitrogen are often magnetically

non-equivalent, e.g. DMF

46
 O
CH3 O
H N + CH3
H N
CH3
CH3

The free rotation of C-N bond is slower than the

time required for an NMR transition

 Two methyl groups are not magnetically equivalant

47
25° 100° 120° 150°

Figure 35. The appearance of the methyl resonance of

DMF in various temperatures

48