Nuclear Magnetic Resonance

Chem 634
T. Hughbanks

1
 Books, Web sites, etc.
✿ J. Iggo, “NMR Spectroscopy in Inorganic Chemistry”
✿ J. K. M. Sanders and B K. Hunter, “Modern NMR Spectroscopy; A Guide for
Chemists”
✿ H. Friebolin, “Basic One- and Two-Dimensional NMR Spectroscopy”
✿ D. Canet, “Nuclear Magnetic Resonance; Concepts and Methods”
✿ E. A. V. Ebsworth, D. W. H. Rankin, S. Cradock, “Structural Methods in
Inorganic Chemistry”, Chapter 2.
✿ R. S. Drago, “Physical Methods”, Chapters 7, 8, and 12.
✿ For serious NMR students, some excellent on-line resources http://
www.spectroscopynow.com/coi/cda/landing.cda?
chId=5&type=Education
✿ Guillermo Moyna’s good NMR lectures (from which I’ve borrowed some)
http://208.7.154.206/gmoyna/NMR_lectures/NMR_lectures.html
✿ A good site for NMR basics: http://www.cis.rit.edu/htbooks/nmr/
inside.htm
✿ A good site for basic organic spectra and some problems: http://
www.cem.msu.edu/~reusch/VirtualText/Spectrpy/nmr/nmr1.htm
2
 More
Advanced
Inorganic/
Organometallic
Reference

3
 NMR is Broadly Applicable
• Nuclear Magnetic Resonance
• Applies to atoms and molecules with nuclear spin
quantum numbers greater than zero.
• Applied magnetic field induces Zeeman splittings
in spin states, and energy is absorbed from
radiation when the frequency meets the
resonance condition, hν = ∆E ∝ µN × H0
• 1/λ ~ 10–3 cm–1, ν = c/λ ~ 25–500 MHz

4
Spectroscopy: The Big Picture
NMR

5
Basic Aspects of the NMR
Phenomenon

6
 Zeeman interaction for proton
If a proton is placed in a magnetic field, H =
ˆ the proton’s energy will depend on its
Hz z,
mI value. The Zeeman interaction between
the applied field and the magnetic moment of
the proton is illustrated as: For proton:
mI = −1 2
g N = 5.585
E g N µ N H 0 = γ N !H 0 γ N = 26,753
(magnetogyric ratio)
mI = 1 2 (radians • s –1 • G –1 )
H
7
 Sensitivity, Populations
Even at 300 MHz (H = 7.05 T), the
population difference of the two spin states
for a proton is ~10–5. Since other nuclei have
smaller gyromagnetic ratios, they exhibit
even smaller differences at the same field.
Nβ − ∆ E k BT ∆E
= e ! 1− = 0.99999135
Nα k BT
(H = 7.05T; T = 298K)

8
 Time Scale
• NMR is generally considered to be a
slow technique, with a characteristic
time scale, τ ~ 10–7 s. (Recall, 1/τ = ν ~
100 MHz.)
• Molecular events occurring in times
much faster than 10–4 s or less are “time
averaged” in NMR (a more careful
distinction to come later).

9
 Miscellaneous Familiar Matters
• For solution spectra, the immediate chemical/structural
information is conveyed by the chemical shifts and the
spin-spin couplings.
• Nuclei with I >1/2 have quadrupole moments - even
solution spectra are broadened when such nuclei
experience electric field gradients.
• The ratios of resonance frequencies for a given field are
equal to the ratios of the gyromagnetic constants: γ A/γ B =
νA/νB. For example, on a “300 MHz spectrometer”, 13C
spectra occur at 75.44 MHz since γ 13C/γ 1H= 6728/26,753 =
75.44/300.
(It would be better to call a “300 MHz
spectrometer” a 7.046 T spectrometer.)

10
 Chemical Shift Scale

ν − ν TMS 6 ν − ν TMS
δ= δ ppm = 10 ×
ν TMS ν TMS

• In order to make NMR data independent of the

field used, chemical shifts are reported relative
to a standard (usually TMS for 1H and 13C).
• Since the shifts are generally small, they are
always given in parts per million (ppm).

11
 Peak differences often in Hz
• It turns out to be more physically useful to
think about differences between energies of
NMR transitions in terms of differences in
frequencies, e.g., ν2 – ν1.

6 ν 2 − ν TMS 6 ν1 − ν TMS 6 ν 2 − ν1
δ 2 − δ1 = 10 × − 10 × = 10 ×
ν TMS ν TMS ν TMS
ν TMS
⇒ ν 2 − ν1 = 6
(δ 2 − δ1 )
10

12
 Resonance, Larmor Frequency
∆ E = γ N !H 0 = hν L
(γ N is the gyromagnetic ratio for the nucleus in question)
γN
ν L is the Larmor frequency: ν L = H0 ; ω 0 = γ N H0
2π
γN
including chemical shift: ν =
2π
(
H0 1 − σ )
• NMR transitions are stimulated (absorption and
emission) by an additional oscillating
(electro)magnetic field, H1, is applied at the
Larmor frequency.
• Shielding is proportional to the applied field -
hence the units of chemical shift: ppm.
13
 More Familiar Matters
• Resonance frequencies for two
interacting nuclei are given by
E = −h∑ ν A mA + h ∑ J AB mA mB
A A< B
where mA is the z-component the spin on A, and J AB
is the coupling constant for A interacting with B.

• This expression applies when chemical

shift differences are much greater than
couplings, |νA – νB| >> JAB .

14
Basic Spectra - 1H

15
Basic Spectra - 1H

16
Basic Spectra - 1H

17
Basic Spectra - 1H

18
19
 Notation for labeling nuclei
• Chemically and magnetically equivalent nuclei given the same
label. (e.g., A)
• Chemically, but not magnetically equivalent nuclei given primes.
(e.g, AA′ for two, AA′A′′ for three, etc.)
• Nuclei with small chemical shift differences (smaller or comparable
to coupling between them) given alphabetically close labels (e.g., A,
B, C, D, etc.)
• Inequivalent nuclei with large chemical shift differences given
alphabetically distant labels (e.g., AMX, for three)
• One can describe a mix of types of nuclei
– A2BMXY is a six-spin system with two equivalent nuclei (A), strongly
coupled (compared to ∆νAB) to one nucleus B, weakly coupled to one
nucleus M (vs ∆νAM) and very weakly coupled to X & Y
– M is weakly coupled to all nuclei
– B is only strongly coupled to A
– X & Y are strongly coupled to each other and weakly to all other nuclei

20
 A (disastrous) problem from the 2008 Final

On the next slide is a fairly accurate simulation of the line

1
positions and intensities observed for the H NMR
spectrum of methylethylketone, CH3COCH2CH3, measured
on an old continuous-wave 60 MHz (1.4093 T) NMR
instrument (the TMS reference is not shown). Assign the
spectrum, and in the blank space below the spectrum, draw
an analogous stick-like spectrum that shows, as accurately
as possible, what the spectrum would look like if recorded
on a more modern 300 MHz (7.0463 T) instrument. Be
careful to accurately place the positions of the peaks and
their relative intensities.

21
 O

1HNMR,
60 MHz

3.0 2.0 1.0 0

δ (ppm)

1H NMR,
300 MHz

3.0 2.0 1.0 0

δ (ppm)
22
An “unknown” example - 1H

23
An “unknown” example - 1H

24
An “unknown” example - 1H

25
An “unknown” example - 1H

26
Even AMX can be
a little complicated

HX HA
Ph HM

27
Basic Spectra - 13C

28
Inorganic and organometallic chemists
must look well outside this range,
e.g. aromatic compounds usually lie
between δ 110-170 ppm, but π-bonded
arenes may be shifted by up to 100 ppm
further
13C CI δ = -293 ppm
4
13C M(CO) δ=
x
170-290 ppm
13C L M=CR δ = 250-370 ppm
x 2
Interstitial carbides are highly deshielded:
13C [Zr CX ]L δ = 450-520 ppm
6 12 6

29
An “unknown” example - 1H & 13C
13C

C4H10O2

1H

30
 An “unknown”
example - 1H & 13C 13C

C11H12O2

1H

31
 Origins of Chemical Shifts (Shielding)
(
H = H0 1 − σ ) ; σ = σd + σ p
e2 x2 + y2
( )
σ d zz =
2mc 2
0
r 2
0

⎧ 2Lz 2Lz ⎫
⎛ e! ⎞
2 ⎪⎪ 0 Lz n n 3 0 0 3 n n Lz 0 ⎪
⎪
σp ( )
zz = − ⎜ ⎟ ∑
⎝ 2mc ⎠ n ⎪
⎨
En − E0
r + r
En − E0
⎬
⎪
⎪⎩ ⎪⎭

• Shielding consists of a diamagnetic (σd) and paramagnetic (σp)

response of the electrons to the applied field.
• σd arises from a first-order effect, reflecting the electron density
distribution in the ground state. (Often dominant in proton spectra.)
• σp arises from a second-order mixing of paramagnetic excited states
into the ground state by the applied field (much like TIP). Often
dominant for other nuclei.
32
 4.7%
100%
33.7%

33
 Relaxation Iggo, Sec .1-10
• Refers to processes by which spins nonradiatively
lose energy
• The phenomenon of relaxation is crucial to NMR. In
the (obsolete) continuous wave method, signals
would rapidly saturate because spin populations
can become equal. In FT-NMR, relaxation is
necessary to bring system to equilibrium between
pulses.
• T1: spin-lattice relaxation, dissipation of energy to
surroundings (non-spin degrees of freedom)
• T2: spin-spin relaxation, transfer of energy to other
spins. T1 ≥ T2
• Quadrupole moments, Q, cause T2 to shorten
greatly, leading to line-broadening
34
 Correlation times and Relaxation

Relaxation effects depend on the frequency spectrum of the local fields

experienced by a nuclear spin. The correlation time, τc, is a
characteristic time scale of fluctuations (due to molecular tumbling ~
rotational Brownian motion) in solution. Relaxation is most efficient
when 1/τc ~ ν.
35
36
37
 The NMR Experiment
http://www-keeler.ch.cam.ac.uk/lectures/
Chapter 3: The Vector Model
Chapter 4: Fourier Transformation and Data Processing
Chapter 5: How the Spectrometer Works

38
 NMR Spectrometers
• Typical now are 5-10T magnets - must
be very stable and highly homogeneous
• RF transmitter and pick-up coils
• Decoupler
• Recording device, computer for Fast
Fourier Transforms, FID storage

39
 More Experimental Aspects
• Must lock on a resonance frequency of a nucleus that is not
the one being measured to maintain stability. 1H NMR uses
2H (i.e., D).

• Probe is at the center of the field and consists of a sample

holder with coils. The radiofrequency of the nucleus under
investigation is applied to the sample via the transmitter coil,
and, at resonance, a voltage is induced in the receiver coil
which detects sample magnetization.
• The sample is spinning during the experiment to ensure
optimum field homogeneity. The sample holder acts as a
turbine driven by compressed air.
• Most instruments have another coil used as decoupler and a
variable temperature device.

40
 NMR Instrumentation Magnet - Normally superconducting.
Some electromagnets and
permanent magnets (EM-360,
EM-390) still around.
Ho Frequency generator - Creates the
alternating current (at ωr) that
induces H1. Continuous wave or
pulsed.
N S Magnet
Detector - Subtracts a constant base
frequency very close to ω0 that is
H1 essentially the frequency of the
“rotating frame”, ωr. The output
Recorder
Frequency frequencies, ω0 – ωr, are much
Generator lower and much easier to deal
with. (In this respect, an NMR
Detector
machine is much like a an
expensive FM radio.)
Recorder - XY plotter, oscilloscope,
computer, etc.

41
 Macroscopic Magnetization
The molar bulk nuclear magnetization (H 0 = applied field),
2
µ N 2 2 NA
2
M = gN N A
I(I + 1)H 0 = γ N ! ⎡⎣ I(I + 1) ⎤⎦ H 0
3k BT 3k BT

• This applies to a mole of nuclei with

spin I and is derived in exactly the same
way as for Curie’s law for electronic
magnetic moments.
• It is very small, since µN = (µB/1836).

42
Resultant Magnetization
• At equilibrium, there
is no transverse
component to the
magnetization.
• In many instances,
the behavior of M0 is
envisioned as it
“evolves” in NMR
experiments.

Iggo, Sec .1-12

43
 Resultant Magnetization
• At equilibrium, there is a slight
excess of “spins-up”, but no net
transverse component to the
magnetization.
z z

z
=

Mo
x
y
y
Bo

x
= “0”

Adapted from http://tonga.usip.edu/gmoyna/

NMR_lectures/NMR_lectures.html, lecture 1

44
Basic Pulse Experiment -
Assume one type of
nucleus
a) Begin at equilibrium
magnetization for the
applied field.
b) Perturb the system
with a transverse
RF pulse and M will
precess about the z-
axis at the Larmor
frequency, ω0 = γ H0.

45
 Basic Pulse Experiment - Assume one type of nucleus
a) Apply a perturbing field, H1, oscillating at angular frequency ω 0 along
the x-axis. The energy source is an oscillating electromagnetic
radiation generated by an alternating current:
z
H1 = C * cos (ωot)
Mo
x
H1
Ho
y
i
Transmitter coil (y)
b) The linear oscillating field H1 can be described as a superposition of
two fields rotating away from the x-axis:
y y y
-ωo +ωo

x = x + x

c) We can restrict attention to the circular component moving in the

same direction as the precession of M.

46
 Basic Pulse Experiment
ω 0 = γ N H0

• H1, oscillating at angular

frequency ω 0 in the
laboratory frame,
The relative orientations of follows M’s motion
the magnetization, M, its xy around the z-axis and
component, Mxy , and the applies a torque to M
rotating RF field, H1. that drives M into the
xy-plane.

47
Motion of M in the Lab Frame
The magnetization
vector, M, traces a
complex path (referred
to as nutation) in the
laboratory frame when
rf field H1 is applied.
Most vector diagrams of
M therefore refer the
rotating frame -
rotating at the Larmor
frequency.

48
Motion of M in the Lab Frame
49
 View in the rotating frame
• If we adopt a frame of
reference that rotates at an
angular frequency at (or
very near to) ω 0, H1 and M
are fixed (or nearly fixed) in
general, γ H1 ≫ γ H 0 − ω r
Intime.

• If H1 is applied as a pulse
for time tp (~ 10 µs), the ‘tip
H1 = H1 (ω r ) ; ω r ! ω 0 = γ H 0
angle’, θ, through which M
is tilted is θ = γ H1tp.
It is understood that ‘tip angle
diagrams’ refer to the rotating • Usually, the time of the
frame. pulse is referred to by the
tip angle (i.e., as a π/2
50
 More than one kind of nucleus
• Inequivalent nuclei have
different Larmor frequencies.
• It is therefore impossible for
H1(ω r) to be exactly “on
resonance” with all the lines
in the spectrum.
• The greater a peak is offset
from ω r, the greater those
nuclei’s magnetizations will
be from those which are on
Effect of a π/2 pulse on M paths: resonance.
path a: on resonance (ω a = ω r) • For nuclei b, c, and d, this
path b: γ H1 = 2|ω b – ω r| pulse is “soft” and not really a
path c: γ H1 = |ω c – ω r| π/2 pulse. To make the pulse
path d: 1.5γ H1 = |ω d – ω r| “hard”, we want to increase
A,B,C,D: respective effective field H1 and shorten tp.
directions.
51
 Hard Pulse - Example
• Consider a proton
spectrum spanning 10 ppm
to be measured on a 500
MHz spectrometer
• Put the transmitter (source
of H1(ω )) near 5 ppm
• Maximum offset ≈ 5 × 500
Hz = 2500 Hz
• On a typical spectrometer,
a 90˚ pulse might last
about 12 µs.
Is the RF power “strong”
over all the spectrum?
52
 Hard Pulse - Example
• Consider a proton spectrum spanning 10 ppm to
be measured on a 500 MHz spectrometer
• Put the transmitter (source of H1(ω )) near 5 ppm
• Maximum offset ≈ 5 × 500 Hz = 2500 Hz
• On a typical spectrometer, a 90˚ pulse might last
about 12 µs. Calculating,
The tip angle is given by θ tip = γ H1tpulse
θ tip π 2
Therefore, ω1 = γ H1 = = = 1.3 × 105 s −1 = 130000 radians s −1
tpulse 12 × 10−6 s
Maximum offset is 2π × 2500 Hz = 15700 radians s −1

• RF field frequency is about 8 times the offset.ü

53
Data Acquisition
• After the pulse is applied,
data is collected as “Free
Induction decays” (FIDs)
until the signal begins to
descend into the noise.
• FIDs are Fourier
transformed to pull our their
characteristic frequencies
(or their differences with
respect to a reference
frequency).

54
 Basic 1-Pulse FT NMR Experiment

• Summary: After the pulse, the time-domain FID

data is collected over the “acquisition time”. Then
there is a delay time to allow the spin system to
return to equilibrium…then another pulse…

http://www.scs.uiuc.edu/~mainzv/Basics/basics.htm
55
 Peak intensities and Relaxation times
The intensity observed for a given resonance (IA)
is proportional to the extent to which the pulse
induced magnetization decays to its equilibrium
value:
( )
I A ∝ ( M 0 − M z (0) ) 1 − e
−τ T1A

⎡⎣ A⎤⎦ I A −τ T
1 − e 1B
= × −τ T1A
⎡⎣ B ⎤⎦ I B 1− e
M0 is the equilibrium longitudinal magnetization,
Mz(0) is the longitudinal magnetization after the
perturbing pulse, τ is the acquisition time, and T1A
is the spin-lattice relaxation time for nucleus A.
See Canet, Chapter 4.
56
 Measuring T1: Inversion Recovery
• Measurement of T1 is important, as the relaxation rate of different
nuclei in a molecule can tell us about their local mobility. We cannot
measure it directly on the signal or the FID because T1 affects
magnetization we don’t detect. We use the following pulse
sequence: 180y (or x) 90y
acquire

tD

z z
• analyze after the π pulse:

x 180y (or x) x tD

y y

• we are letting the signal decay by different amounts exclusively

under the effect of longitudinal relaxation (T1), we’ll see how different
tD’s affect the intensity of the FID and the signal after FT.

57
tD = 0 z z
Inversion
x 90y x FT
Recovery,
y y cont.
Depending on the tD
tD > 0 delay we use we get
z z
signals with varying
intensity, which
x 90y x FT depends on the T1
relaxation time of the
nucleus (peak) we
y y
are looking at.

tD >> 0 z z

x 90y x FT

y y

58
59
 Inversion
N N
at 40oC
Recovery,
cont.

If we plot intensity
Intensity ( )

versus time (td), we I(t) = I∞ * ( 1 - 2 * e - t / T1 )

get the following:

time

60
 Spin Echo - T2 measurement
• Measurement of T2 can in principle be performed by
calculating the decay in the FID envelope (which
determines the line widths) because the signal on
Mxy, in theory, decays only due to transverse
relaxation. In practice, however, contributions due to
field inhomogeneity can dominate.
• The spin-echo pulse sequence allows us to avoid
contributions inhomogeneous broadening:
90y 180y (or x)
acquire

tD tD

61
 z y

Spin echoes (continued)

x
• We do the analysis after the 90y pulse: ≡ x
y

y y
tD

y
tD
x
x
180y (or x) x

refocusing
•Now we return to <xyz> coordinates: dephasing
y z

x
≡
y

62
 The 180˚ pulse: refocusing

Vectors that lag in the delay

are jumped ahead in the 180˚
pulse. The second delay
refocuses them.

• Different nuclei in the sample move away from the y-

axis (to which M is tipped in the π/2 pulse) at different
rates because of chemical shift differences and field
inhomogeneity. The Hahn spin-echo sequence allows
them to refocus at the –y axis. But transverse
relaxation still attenuates the magnitude of M.
63
• If we acquire an FID
Spin echoes (continued)
right after the echo,
the intensity of the

Intensity ( )
signal after FT will
affected only by T2
relaxation and not by I(t) = Io * e - t / T2
dephasing due to an
inhomoge-neous Bo.
We repeat this for
different tD’s and plot
time
the intensity against
2 • tD. In this case it’s
a simple exponential
decay, and fitting

N N
at 90oC

64
A Little Theory of 1-D NMR

65
 Origins of Chemical Shifts (Shielding)
(
H = H0 1 − σ ) ; σ = σd + σ p
e2 x2 + y2
( )
σ d zz =
2mc 2
0
r 2
0

⎧ 2Lz 2Lz ⎫
⎛ e! ⎞
2 ⎪⎪ 0 Lz n n 3 0 0 3 n n Lz 0 ⎪
⎪
σp ( )
zz = − ⎜ ⎟ ∑
⎝ 2mc ⎠ n ⎪
⎨
En − E0
r + r
En − E0
⎬
⎪
⎪⎩ ⎪⎭

• Shielding consists of a diamagnetic (σd) and paramagnetic (σp) response of the

electrons to the applied field.
• σd arises from a first-order effect, reflecting the electron density distribution
in the ground state. (Often dominant in proton spectra.)
• σp arises from a second-order mixing of paramagnetic excited states into the
ground state by the applied field (much like TIP). Often dominant for other
nuclei.

66
 Chemical Shift Example:

[Zr6BCl12(MeCN)(6-x)Clx]1-x

11B NMR spectra for Rb5Zr6Cl18B in acetonitrile with (a) no added ligand, (b) 6
eq. added TlPF6, and (c) 10 eq. added PPNCl. Labeling on the peaks (x = 0 − 6)
indicates the number of terminal chlorides in [(Zr6BCl12)(NCCH3)6-xClx]1-x.

67
Chemical Shift Example:

[Zr6BCl12(MeOH)(6-x)pyx]+
• 11B spectrum of
[Zr6BCl12(MeOH)6]+
in methanol solvent,
to which pyridine
was added until the
pyridine mole
fraction was 5%.

68
 More on Spin-spin Coupling
• The nuclear spin Hamiltonian for two interaction
nuclei, A and X, is

( )
H = −h ν A I Az + ν X I Xz + hJ AZ I A • I X

where I Az and I Xz are operators for the

z-component the spin on A and X , and J AX is
the coupling constant for A interacting with X .
• This Hamiltonian will yield the energy expression
given earlier (when chemical shift differences are
much greater than couplings, |νA – νB| >> JAB .

69
 AX
1st-Order Spectral Case
( )
spin
states H = −h ν A I Az + ν X I Xz +hJ AZ I A • I X
|ββ〉 +ν0 [1–1/ 2(σ A+ σX )]ν0
|ββ〉 [1–1/ 2(σA + σX)]ν0 + 1/ 4JAX

[+1/ 2(σX – σA )]ν0

|βα〉 [+1/ 2(σ X– σA )]ν0– 1 /4 JAX
|βα〉 |αβ〉
[+1/ 2(σA – σX )]ν0
|αβ〉 [+1/ 2(σ A– σX )]ν0– 1 /4 JAX

[–1+1/ 2(σA + σX)]ν 0 [–1+1 /2 (σA + σ X)]ν0 + 1/4 JAX

|αα〉
|αα〉 –ν0

bare shielded spin-spin

nuclei nuclei coupling In the first-order case
1st-order
where |νA – νX| >>
JAX, mixing of the
H H
spin functions is
neglected.
70
 2nd-Order Spectral Case
[1–1/ 2(σ A+ σX )]ν0+ 1 /4JAX |ββ〉 |ββ〉 hJ AX I A • I X =

2
2
⎣ ( )
hJ AX ⎡ 12 I A+ I X− + I A− I X+ + I Az I Xz ⎤
⎦
4 4
sin θ |αβ〉 + cos θ |βα〉
[+1 /2 (σX– σ A)]ν0 – 1/ 4JAX |βα〉
δ = (σX – σA )ν0
[+1 /2 (σA– σ X)]ν0 – 1/ 4JAX |αβ〉
cos θ |αβ〉 – sin θ |βα〉
mixes αβ and βα
3 3
1 1

[–1+1/ 2(σA + σX)]ν 0 + 1/ 4JAX [J2 + δ2] 1/2

|αα〉 |αα〉
2θ J

spin-spin spin-spin
coupling coupling In the 2nd-order
1st-order 2nd-order
3 2 case, |νA – νX| ~ JAX,
43 21 4 1
mixing of the spin
H H
functions leads to
intensity changes
I1,4 ~ 1 – sin2θ
See Drago, Chapter 7. I2,3 ~ 1 + sin2θ
(the rooftop effect)
and line shifting.
71
Range of cases

72
Miscellaneous Examples

73
Coupling Examples
Coupling of
spin-1/2
nuclei works
in pretty
much the
same way in
all cases.

74
Coupling to non-spin-1/2 Nuclei
73Ge (I = 9/2, 8%
abundance) couples
to equivalent
protons in 73GeH4.
(1H spectrum)

75
 Coupling to
Quadrupole
Nuclei

• Because spin-spin coupling

induces spin wavefunction
mixing, the relaxation of a
quadrupole nucleus is partially
“transferred” to spin-1/2 nuclei
to which it is coupled.

76
Si2H6 (1H spectrum)
29Si
(I = 1/2, 4.7%
abundance)

77
Si2H6 (1H spectrum)
29Si
(I = 1/2, 4.7%
abundance)

78
 [Zr6BCl12(PEt3)6]+ + ?

a) 11B
spectrum of
[Zr6BCl12(PEt3)6]+
b) 31P plus an impurity.
b) 31P spectrum of
[Zr6BCl12(PEt3)6]+
plus an impurity.
a) 11B

What is the impurity?

11B (I = 3/2, 81.2% abundance), 10B (I = 3, 18.8% abundance)

79
 1st and 2nd-
order spectra

(a)

(b) a) 360 MHz 1H spectrum for

CH3CH2SPF2. (1st order)
b) 80 MHz 1H spectrum for
CH3CH2SPF2. (2nd order)

80
Correlations like the well-known Karplus
relation shown here ultimately derive
Coupling:

from the manner in which s-electron
density is involved in wavefunctions that Structural
spread over two coupled nuclei.
Correlations
For 3-bond coupling constants
the empirical relation here is useful:
3J
XY
= Acos 2φ + Bcos φ + C

81
JAM > JAX > JMX
vicinal
protons

HX HA
Ph HM

82
 trans-Rh(CO)Cl{Ph2PCH2P(O)Ph2}2:

31P{1H}: First- and Second-order Coupling

103Rh I = 1/2 abundance = 100%

83
 Coupling:

Correlations ultimately derive from
the manner in which s-electron
density is involved in wavefunctions
Structural
that spread over two coupled
nuclei.
Correlations

84
A Typical (Simple) Structural
problem

85
 Chemical Shift Equivalence

(isochronous nuclei)
(1R,3R)-dl Hc
Hd
• Two isomers of 1,3-
Ph
dibromo-1,3-
Ph
diphenylpropane
Br
Ha Hb • How many chemical-
Br
shift equivalent sets
Hc
Hd
of aliphatic protons
(1S,3R)-meso Ph in each isomer?
Ph

Hb
Ha Br
Br

86
 Magnetic (In)equivalence
p-fluoronitrobenzene
NO2 • Magnetically equivalent
nuclei are coupled
Hc Hd
equally to every third
nucleus in the spin
Hb
system.
Ha
• In each molecule the
F
protons are chemical
difluoroethylenes shift equivalent?
Fb Hb Fa Fb Fa Hb • Which sets are
magnetically
Fa Ha Ha Hb Ha Fb
equivalent?

87
 Magnetic (In)equivalence
C5H5N (simulated)
• Magnetically
equivalent nuclei are
coupled equally to
every third nucleus in
the spin system.
• The “unknown” here
is an easy one, but
the spectrum is more
complicated than you
might have expected.

88
 H
Magnetic F
F
(In)equivalence H

Fb Hb

1H spectra
Fa Ha

89
 Notation for labeling nuclei
• Chemically and magnetically equivalent nuclei given the same
label. (e.g., A)
• Chemically, but not magnetically equivalent nuclei given primes.
(e.g, AA′ for two, AA′A′′ for three, etc.)
• Nuclei with small chemical shift differences (smaller or comparable
to coupling between them) given alphabetically close labels (e.g.,
A, B, C, D, etc.)
• Inequivalent nuclei with large chemical shift differences given
alphabetically distant labels (e.g., AMX, for three)
• One can describe a mix of types of nuclei
– A2BMXY is a six-spin system with two equivalent nuclei (A), strongly
coupled (compared to ∆νAB) to one nucleus B, weakly coupled to one
nucleus M (vs ∆νAM) and very weakly coupled to X & Y
– M is weakly coupled to all nuclei
– B is only strongly coupled to A
– X & Y are strongly coupled to each other and weakly to all other nuclei

90
 Examples

(ignoring phenyl groups)
(1R,3R)-dl Hc
Hd
• AA′MM′
Ph

Ph

Br
Ha Hb
Br

Hc
Hd
• ABM2
(1S,3R)-meso Ph

Ph

Hb
Ha Br
Br

91
 More Examples
P-fluoronitrobenzene
NO2

Hc Hd
• AA′BB′ (in a sufficiently
high field, AA′MM′ )
Ha Hb

difluoroethylenes
Fb Hb Fa Fb Fa Hb

Fa Ha Ha Hb Ha Fb

all AA′XX′ (AA′MM′ equally good)

92
Characterize indicated protons as to chemical-
shift and/or magnetic equivalence

H H H3C H H

C C C CH(CH3)(C2H5)
H H H3C H H

CH(CH3)2 Cl Cl
H H O

Cl I
H3C CH3 H H

93
 More Examples (31P)
PMe3 Cl PA Cl
Cl PEt3 Cl PB
M M A2B2 M M
Cl Et3P Cl PB
PMe3 Cl PA Cl

• Both 31PMe3 couple to each of the 31PEt3 in

an equivalent fashion (and vice versa).

94
 More Examples
PMe3
PA Cl
PMe3 Cl Cl
PEt3 Cl PB'
Cl Cl M Cl
M M
≡ M M
Me3P M PEt3
Cl Me3P Cl PA'
PEt3
PEt3 Cl PB Cl
Cl
AA′BB′

• The 31PMe3 couple to each of the 31PEt3 differently

(and vice versa), ∴ magnetically inequivalent.
• Sample data:
• JAB = JA′B′ = 104 Hz
• JAA′ = JA′A = 20 Hz
• JBB′ = JB′B = 19.2 Hz
• JA′B = JAB′ = JBA′ = JB′A = 23 Hz
95
Expected 31P {1H} Spectrum
PA Cl
Cl PB'
M M
Cl PA'
PB Cl
AA′BB′
Sample data:
– JAB = JA′B′ = 104 Hz
– JAA′ = JA′A = 20 Hz
– JBB′ = JB′B = 19.2 Hz
– JA′B = JAB′ = JBA′ = JB′A = 23
Hz

96
 Dynamic NMR

See Chapter 7,
NMR and Chemistry, 4th Edition, J.W. Akitt and B. E. Mann.

97
 Time Scale
∆ E = γ N !H 0 = hν L
γN
νL = H0 ; ω 0 = γ N H0
2π
γN
including chemical shift: ν =
2π
(
H0 1 − σ )
• NMR is generally considered to be a slow
technique, with a characteristic time scale, τ ~ 10–
7 s. (Recall, 1/τ = ν ~ 100 MHz.)

• This is actually much faster than rates usually

measured with NMR. Reactions with half-lives of
10–2 s to 10–3 s are more typical, I.e., the
difference between resonance frequencies.
98
A Familiar
Example -
Proton
Exchange

99
 Thermodynamic and Kinetic
Exchange Parameters
k
!!!
A ↽!!
A⇀
! B
k B

Well below the coalesence point), the

individual line widths are given by:
kA 1 kB 1
∆ν A = = ; ∆ν B = =
π πτ A π πτ B
In the limit of fast exchange (above the
coalesence point), the line width is given by:
4π p A pB (δν AB )2
∆ν =
k A + kB
p A and pB are the fractional populations of sites A and B.

100
 O O–
Hindered
Rotation
CH3 CH3
H N H N

CH3 CH3

A 2-site example illustrating different line-shape regimes in

a dynamic process amenable to NMR study.

Near Fast exchange

Coalescence

Intermediate exchange

Slow exchange

Stopped exchange 7.9 Hz

101
 Cyclohexane
Interconversion
Near
Fast
exchange Another 2-site example
illustrating different
line-shape regimes in
Coalescence a dynamic process
amenable to NMR
study.
Intermediate
exchange
H H D D
H H D
D D H D
H
H H
D D D
D H H
Slow D D H H
exchange

Stopped exchange

102
 TC and kC
If (a) the exchange process is first-order,
(b) there is no coupling between exchanging
nuclei, and
(c) the two singlets have equal intensities:
For the coalescence temperature, TC , the rate constant, kC , is
π ∆ν
kC = ≅ 2.22 ∆ ν
2
∆ ν is the chemical shift difference (in Hz) in the absence of
exchange (determined at low temperature but extrapolated to high T).
• Even when (a), (b), and (c) are not exactly
fulfilled, this is usually a decent estimate for kC.

103
 TC and kC
• Coalescence is
defined as the point
at which the minimum
between the high
temperature peaks
becomes a flat
plateau.

104
 The Slow Exchange Regime
1
W1/ 2 = 1 1 1 k
π T2 W1/ 2 = + = +
when spin-spin relaxation π T2 πτ ex π T2 π
is the mechanism where k is the rate constant for exchange
controlling a spin's lifetime When exchange is
Linewidth determined by occurring there are two
time a spin spends at one mechanisms that shorten
location (nucleus) the lifetime of the spin state

⎡ 1 ⎤
(
∴ k = π ⎢ W1/ 2 −
ex
)π T
⎥ ⎣ (ex
) (
= π ⎡ W1/ 2 − W1/ 2 ⎤
0⎦
)
⎣ 2⎦

fairly accurate when W1/ 2( )ex

is substantially larger than W1/ 2( )0
105
 Fluxional Cp Rings
• The η1- and η5-Cp
proton resonances
coalesce at 36 ˚C.
(What process must
be quite rapid even at
-27 ˚C?)

Ti H
H

106
 TC and kC - more
• When expressed in ppm, chemical shifts are
field independent. But ∆ν is in Hz, which means
that ∆ν ∝ H. Therefore, TC and kC increase with
the field used in the NMR experiment (and the
highest available field may not be the most
appropriate).
• Coupling between exchanging nuclei can be
handled: If nuclei A and B are exchanging and
are coupled (with constant J AB ) kC is
π ∆ν
( )
2 2
kC = ≅ 2.22 ∆ν + 6J AB
2
107
 An example
with Coupling
• HA and HB are clearly
inequivalent at -55 ˚C,
but are equivalent in
the fast exchange
regime at 35 ˚C.
• How would this study
have changed if
carried out on a 300
MHz instrument?

108
 Complete Line Shape Analysis
• Record spectra at different temperatures, e.g.,
– 3 slow-exchange spectra (incl. 1 stopped-exchange)
– 5-10 spectra in coalescence regime
– 3 spectra in near-fast and fast regime
• Analyze spectrum in stopped exchange regime
– Get ν’s, J’s, line-widths (∆ν1/2’s)
• Calculate spectra in the coalescence regime,
varying k(s) until observed and calculated
spectra match. Repeat at other temperatures.
• If necessary, calculate spectra in fast-exchange
limit.

109
Evidence for Berry Pseudorotation
Observed and calculated 36.43 MHz
31P{1H} spectra of [Rh{P(OMe) } ]+
3 5
in CHClF2/CH2Cl2 (9:1) at –114 ˚C.
P1 P2
P4 P4
Rh P2 Rh P1
P3 P3
P5 P5

pairwise exchange (turnstile) mechanism

P1 P3

P4 P1
Rh P2 Rh P2
P3 P5

P5 P4

Berry pseudorotation (P4 pivot)

110
 Activation Parameters
• Use of the Arrhenius plots (lnk vs. 1/T) are a lot of work
since they require data for a range of temperatures (many
measurements and full line-shape analyses)
• Estimate for ∆G‡ using the Eyring equation is easy with TC in
hand:
k BT − ΔG ‡ RT k BT ΔS ‡ R − ΔH ‡ RT ‡
⎧⎪ ⎛ k ⎞ ⎫⎪
k =ℵ e =ℵ e e or ΔG = RT ⎨23.759 + ln ⎜ ⎟ ⎬
h h ⎪⎩ ⎝ T ⎠ ⎪⎭
⎛ k BT 12 −1
⎞
⎜ at T = 298.15 K, = 6.21 × 10 s , ℵ is usually taken to be ~ 1⎟
⎝ h ⎠
An Eyring plot, ln(k/T) vs. 1/T, would should yield ∆H‡ and ∆S‡,
but again, much more work. WARNING: This approach is
still fraught with the potential for large errors, because the
range temperatures on can measure is small, chemical shift
dependence on T, linewidth misestimates, poor T calibration,
and broadening due to unresolved coupling (see Akitt &
Mann).
111
 More Accurate Activation Parameters
Better activation parameters can be
obtained from NMR kinetic studies:
(1) Use different spectrometers, with
different frequencies. The frequency
difference between resonances
varies with field strength when the
peak differences are due to chemical
shifts (only the ppm values remain
the same). For this reason, a rate
study might be better carried out on
a lower field instrument.
(Coalescence occurs at a lower
temperature in lower field.)
(2) Different nuclei might be used (see
example).
(3) Different methods are useful in different
regimes; e.g., lineshape analysis when
rates are within an order of magnitudes
of the coalescence rate and
⎛ k ⎞ ΔH ‡ ⎛ 1 ⎞ ⎛ ΔS ‡ ⎞
ln ⎜ ⎟ = ⎜ ⎟ −⎜ + 23.759⎟
magnetization transfer for lower ⎝T⎠ R ⎝T⎠ ⎝ R ⎠
temperatures with slower rates.

112
 H1 FeCp(CO)2
How does the ring whiz?
H1-5
(5) (2)

(4) (3)

A
? η5-Cp

A
Fe
B H1
A B

Fe

Peaks at δ ≈ 6.0 (B) & 6.3 (A) are assigned to H3,4 &
Fe
H2,5, respectively.
A resonances collapse faster than B resonances.
Mechanism? See problem set!
113
 Competing
Mechanisms?
• At -3˚C, the COD ethylenic
protons and the diastereotopic
(CH3)P are not exchanging.
• At 67˚C, the COD ethylenic
protons are exchanging, but the
diastereotopic (CH3)P groups
are not.
• At 117˚C, the COD ethylenic
protons and the diastereotopic
(CH3)P are both exchanging.
CH3
H3C
CH3 HB
P
C6H5
H3C Ir
P HB
H3C HA
C6H5

HA

114
 Competing
Mechanisms?
• At -3˚C, the COD ethylenic
protons and the diastereotopic
(CH3)P are not exchanging.
• At 67˚C, the COD ethylenic
protons are exchanging, but the
diastereotopic (CH3)P groups
are not.
• At 117˚C, the COD ethylenic
protons and the diastereotopic
(CH3)P are both exchanging.
CH3
H3C
CH3 HB
P
C6H5
H3C Ir
P HB
H3C HA
C6H5

HA

115
 Short Questions
• Explain each of the following observations.
(a) The 1H spectrum of GeH4 shows 73Ge satellites but the
spectra of GeFH3 and GeClH3 do not.
(b) The 13C-{1H} NMR spectrum of (bis)allylnickel at 200
K shows three resonances, of equal intensity; at 250 K,
only two resonances are observed, in a 2:1 intensity ratio.
(c) The 1H NMR spectrum of rigorously dried 14N-ammonia
is a broad 1:1:1 triplet that becomes broader as the
temperature is lowered; the 1H NMR spectrum of 15N-
ammonia containing a trace of Na15NH2 is a broadened
1:1 doublet that becomes sharper as the temperature is
lowered.

116
 Problem
Reaction of IF7 and SbF5 gives a 1:1
product. The 19F NMR spectrum contains
two sets of resonances: one with 6 lines of
equal intensity; the other with overlapping
patterns of 6 lines of equal intensity and 8
lines of equal intensity, the former being
somewhat stronger. Explain.

121Sb 5/ , 57.3 %, 121Sb 7/2, 42.7 %, 127I 5/2, 100 %

2

117
 Problem
What coupling pattern would you expect
to observe for a single proton coupled to
(a) one and (b) two equivalent 11B nuclei?
(c) Same as (b) but with a “real sample?

11B 3/ , 80.4 %, 10B 3, 19.6 %

2

118
 Problem
The 1H NMR spectrum of GeFH3 consists
of two lines separated by 42 Hz. What
are the relative positions and intensities
of all the lines in the 19F spectrum of
(a) GeDFH2
(b) GeD2FH
(c) GeD3F

119
 Problem
W(CO)6 reacts with NaBH4 to give an
anionic product. Its tetraethylammonium
salt has the empirical composition
C18H21NO10W2. Its 1H NMR spectrum
includes a triplet, intensity ratio 1:6:1, at δ
-22.5 ppm, with a separation between the
outer peaks of 42 Hz. What can you
deduce about the structure of the anion?
183W, S = 1/2, 14.4 %

120