Master STS Chemistry, University of Bordeaux

Master 1, Academic year 2016-2017

4TCH701U: Characterisations
C2M team, ISM, UMR-CNRS 5255, University of Bordeaux

High Resolution
Nuclear Magnetic Resonance
Thierry Toupance

Professor at the University of Bordeaux

Institute of Molecular Sciences, ISM UMR 5255 CNRS,

Molecular Chemistry & Materials Team (C2M)
Tl : 33 (0)5 40 00 25 23
Fax : 33 (0)5 40 00 69 94
email : thierry.toupance@u-bordeaux.fr

4TCH701U: Characterisations
High Resolution Nuclear Magnetic Resonance
C2M team, ISM, UMR-CNRS 5255, University of Bordeaux

Chapter 1
The Physical Basis of Nuclear Magnetic Resonance Spectroscopy
I Quantum mechanics approach
I,1 Nuclear angular momentum and Spin
I,2 Nuclear magnetic moment
I,3 Energy of the nuclei in the magnetic field
The Nuclear Magnetic Resonance phenomenon
I,4 Population of the energy levels
I,5 Creation of the transition and consequences on the macroscopic magnetization
I,6 NMR sensitivity and receptivity
II Vectorial approach and Pulse Fourier Transform Spectroscopy
II,1 Vectorial approach (Bloch model) and rotating frame
II,2 Pulse generation
II,3 The pulse NMR experiments
II,3,1 Effect of the r.f. pulse on the macroscopic magnetization
II,3,2 The F.I.D. (Free Induction Decay) signal
II,3,3 Signal processing: Fourier Transform
II,3,4 NMR spectrum
II,4 Spectrometer
II,5 Relaxation processes

4TCH701U: Characterisations
High Resolution Nuclear Magnetic Resonance
Groupe C2M, ISM, UMR-CNRS 5255, Universit de Bordeaux

Chapter 1
The Physical Basis of Nuclear Magnetic Resonance Spectroscopy
III Examples
III,1 1H NMR
III,2 19F NMR
III,3 31P NMR
III,4 13C NMR
III,5 119Sn NMR

The electromagnetic spectrum

NMR Properties of Spin Nuclei

Isotope

H
H
3
He
13
C
15
N
19
F
29
Si
31
P
57
Fe
77
Se
89
Y
103
Rh
(107Ag)
109
Ag
(111Cd)
113
Cd
(115Sn)
(117Sn)
119
Sn
123
( Te)
125
Te
129
Xe
169
Tm
171
Yb
183
W
187
Os
195
Pt
199
Hg
(203Tl)
205
Tl
207
Pb
3

Natural
Abundance (%)

99.985
1.3 10-4
1.108
0.37
100
4.70
100
2.19
7.58
100
100
51.82
48.18
12.75
12.26
0.35
7.61
8.58
0.87
6.99
26.44
100
14.31
14.40
1.64
33.8
16.84
29.50
70.50
22.6

Magnetic
Moment
/N
4.83724
5.1596
-3.6851
1.2166
-0.4903
4.5532
-0.96174
1.9602
0.1566
0.925
-0.237786
-0.153
-0.1966
-0.2260
-1.0293
-1.0768
-1.590
-1.732
-1.8119
-1.275
-1.537
-1.345
-0.400
0.8520
0.2025
0.111
1.043
0.87072
2.7912
2.8187
1.002

Magnetogyric
Ratio
N
107 rad.T-1.s-1
26.7520
28.535
-20.380
6.7283
-2.712
25.181
-5.3188
10.841
0.8661
5.12
-1.3155
-0.846
-1.087
-1.250
-5.6926
-5.9550
-8.792
-9.578
-10.021
-7.049
-8.498
-7.441
-2.21
4.712
1.120
0.616
5.768
4.8154
15.436
15.589
5.540

NMR
Frequency
(MHz)

Reference

100.000000
106.664
76.182
25.145004
10.136783
94.094003
19.867184
40.480737
3.238
19.071523
4.917
3.172310
4.047897
4.653623
21.215478
22.193173
32.86
35.632295
37.290662
26.35
31.549802
27.81
8.27
17.61
4.161733
2.282343
21.414376
17.910841
57.70
57.633833
20.920597

SiMe4
t-SiMe4
SiMe4
MeNO2 ou [NO3]CCl3F
SiMe4
85% H3PO4
Fe(CO)5
SeMe2
Y(NO3)3aq.
mer-[RhCl3(SMe2)3]
Ag+aq.
Ag+aq.
CdMe2
CdMe2
SnMe4
SnMe4
SnMe4
TeMe2
TeMe2
XOF4
WF6
OsO4
[Pt(CN)6]2HgMe2
TlNO3aq.
TlNO3aq.
PbMe4

Recepticity
D1H

D13C

1.00
5.75 10-7
1.76 10-4
3.85 10-6
0.834
3.69 10-4
0.0665
7.43 10-7
5.30 10-4
1.19 10-4
3.16 10-5
3.48 10-5
4.92 10-5
1.23 10-3
1.35 10-3
1.24 10-4
3.49 10-3
4.51 10-3
1.59 10-4
2.24 10-3
5.69 10-3
5.66 10-4
7.82 10-4
1.06 10-5
2.00 10-7
3.39 10-3
9.82 10-4
0.0567
0.140
2.01 10-3

5.65 103
3.26 10-3
1.00
2.19 10-2
4.73 103
2.10
3.77 102
4.22 10-3
3.01
0.675
0.179
0.197
0.279
6.97
7.67
0.705
19.8
25.6
0.903
12.7
32.3
3.21
4.44
5.99 10-2
1.14 10-3
19.2
5.57
3.22 102
7.91 102
11.4

NMR Properties of Quadrupolar Nuclei

Isotope/Spin

H (I=1)
6
Li (I=1)
7
Li (I=3/2)
9
Be (I=3/2)
10
B (I=3)
11
B ( I=3/2)
14
N (I=1)
17
O ( I=5/2)
21
Ne (I=3/2)
23
Na (I=3/2)
25
Mg (I=5/2)
27
Al (I=5/2)
33
S (I=3/2)
35
Cl (I=3/2)
37
Cl (I=3/2)
39
K (I=3/2)

Natural
Abundance
(%)
0,015
7,42
92,58
100
19,58
80,42
99,63
0,037
0,257
100
10,13
100
0,76
75,53
24,47
93,1

Magnetic
Moment
/N
1,2126
1,1625
4,20394
-1,52008
2,0792
3,4708
0,57099
-2,2407
-0,85433
2,86265
-1,012
4,3084
0,8308
1,0610
0,88313
0,50533

Magnetogyric
Ratio
N
107 rad.T-1.s-1
4,1066
3,9371
10,3975
-3,75958
2,8746
8,5843
1,9338
-3,6279
-2,1130
7,08013
-1,639
6,9760
2,055
2,6240
2,1842
1,2498

Quadrupolar
Moment
28

10 Q/m
2,8 10-3
-8 10-4
-4 10-2
5 10-2
8,5 10-2
4,1 10-2
1 10-2
-2,6 10-2
9 10-2
0,10
0,22
0,15
-5,5 10-2
-0,10
-7,9 10-2
4,9 10-2

NMR
Frequency
(MHz)
15,351
14,717
38,866
14,054
10,756
32,089
7,228
13,61
7,899
26,466
6,126
26,077
7,681
9,809
8,165
4,672

Receptivity
D1H

D13C

1,45 10-6
6,31 10-4
0,272
1,39 10-2
3,93 10-3
0,133
1,00 10-3
1,08 10-5
6,33 10-6
9,27 10-2
2,72 10-4
0,207
1,72 10-5
3,56 10-3
6,66 10-4
4,75 10-4

8,21 10-3
3,58
1,54 103
78,7
22,3
7,52 102
5,69
6,11 10-2
3,59 10-2
5,26 102
1,54
1,17 103
9,77 10-2
20,2
3,78
2,69

I Quantum Mechanics Approach

I, 1 Nuclear angular momentum and Spin
Particle

mass m
charge q
angular momentum L (also named spin)

Lz = mI

Spin is quantized

et

L=

(I(I+1))1/2

with mI : magnetic quantum number

I : whole number or half whole number
mI = I, I-1, , I-n, , -I+1, -I

m
q
L

mI = + 1/2

I = 1/2

mI = - 1/2

cos =

1/2
(I(I+1))1/2

Nuclear spin values

1)

2)

3)

Mass number A odd (Atomic number Z even or odd)

1H (I = 1/2), 13C (I = 1/2), 19F (I = 1/2), 31P (I = 1/2), 11B (I = 3/2)

I half whole number

2H

Mass number A even and atomic number Z odd

(I = 1), 14N (I = 1), 10B (I = 3)

I whole number

Mass number A even and atomic number Z even

12C (I = 0), 16O (I = 0), 32S (I = 0)

I=0

I, 2 Nuclear magnetic moment

Nuclear magnetic moment is quantified
with

= n L
n = gn n : gn Land factor, n Bohr magneton
the magnetogyric ratio n of each nucleus is tabulated

z = n mI

as a result

= n (I(I+1))1/2

and

Ex : I = 1/2 then z(+1/2) = + n and z (-1/2) = - n

I, 3 Energy of the nuclei in the magnetic field

The Nuclear Magnetic Resonance phenomenon
B0 = 0

Degenerated energy levels: spectroscopy is not possible

B0 0

Removing degeneracy: energy of a magnetic dipole in a static magnetic field B0 E = - . B0

If Bx = By = 0 and Bz 0

= z B0 = n mI B0

As a result: for 1H, I = 1/2 and n > 0

E
E(-1/2)

E(+1/2) = - 1/2 (n B0)

tat
-state

= n B0

E(-1/2) = + 1/2 (n B0)

-state
E(+1/2) tat

B0 = 0

B0 0

Planck-Einstein relation = h 0

0 = n B0/2

Larmor frequency

0 = n B0

Larmor angular frequency

Rem : only transitions such as mI = 1 are allowed (selection rules)

General case :

A nucleus with a spin I, located in a magnetic field B0 possess 2I+1 equidistant energy levels
and separated by : E = n B0

Cons : The absorption frequency is proportionnal to the applied magnetic field and to the magnetogyric ratio
E

600 MHz E

depends on the spectrometer used

400 MHz

depends on the nucleus studied

60 MHz

For instance in 1H NMR, n > 0 and I = 1/2

10

15

B0 (T)

600 MHz for14.09T

800 MHz for 18.78 T

I, 4 Population of the energy levels

Let us consider a system of N identical spins located in a magnetic field B0 such as n > 0 and I = 1/2
Due to the static magnetic field B0, magnetic moments are oriented according to two cones of axis B0
z

B0

-state
mI = + 1/2 (tat
)
E

M0

0B0
E == n
nB
E

-state
)
mI = -1/2 (tat

Static magnetization M0 at the equilibrium

The ratio between populations N and N is then given by the Maxwell-Boltzmann statistics
N
N

For instance in 1H NMR, n > 0 and I = 1/2 at 300K

= exp[-(E-E)/kT] = exp[(-nB0)/kT] 1 + (nB0)/kT
kB (Boltzmann constant) = 1.3805 10-23 J.K-1
T: Absolute temperature in K

Very small population difference

at 60 MHz :
at 800 MHz :

h/kT = 9,59 10-6

h/kT = 1,28 10-4

NMR is a low-sensitive technique

I, 5 Creation of the transition and consequences on the macroscopic magnetization

N spins located in B0

magnetic field B0 removes the degeneracy of Zeeman sub-levels

transition frequency 0 = nB0/2

Electromagnetic wave (E1, B1) perpendicular to the magnetic field B0 oscillating at the frequency 0
rotation of the macroscopic magnetization
macroscopic magnetization decreases
Several mechanism: Einstein coefficients
N2

N2

N2
h

N1

N1

N1

Absorption

Spontaneous emission

Stimulated emission

P B1->2N1

P A2->1N2

P B2->1N2

A2->1 << 1 et B1->2 B2->1

Absorption up to saturation

P B1->2 (N1 N2)

relaxation

I, 6 NMR sensitivity and receptivity

Sensitivity:

S=

B02

* N * I(I+1) * NA * C * V *

Natural
Abundance

Avogadro
Number
if is large
B0 is high
high concentration C
low temprature T

Receptivity: inform about the observability of a given nucleus compared to 1H NMR carried out in the same conditions

DX1H =

SX
S1

Examples:

1H

X3
13

NX
100

IX(IX+1)
3/4

: D = 1; 19F : D = 0,836; 31P = 0,0665; 13C : D = 1,76.10-4

119Sn
57Fe

: D = 4,51.10-3; 29Si : D = 3,69.10-4;

= 7,43.10-7; 187Os : D = 2. 10-7

Cons: NMR is a poorly-sensitive technique

Advanced NMR techniques are required

(Pulse Fourier Transform NMR)

II Vectorial approach and Pulse Fourier Transform NMR spectroscopy

II,1 Vectorial approach (Bloch model) and rotating frame
B0
Let us consider a macroscopic magnetization M0

Note the following hypothesis:

a)

Oscillating field B1 can be decomposed into two magnetic components rotating clockwise and anticlockwise
respectively, the resultant of which corresponds to the actual applied field

B1 = B1(r) + B1(l)
desired direction

opposite direction

B1(r) (+ 0) follows the rotation of the magnetization M in the (x, y) plane

b)

Let us consider the rotating frame that rotates at the nuclear precession frequency 0 in the same direction

Analogy with carousels:

Case a)
Case b)

the man riding the horse rotates + 0

for the observer
the man riding the horse is now static
for the observer

As a result :
- for the radiofrequency field (r.f.)
B1(r) component (+ 0 in the laboratory frame) is now static
to be taken into account because oscillation corresponding
to the nuclear precession frequency
B1(l) component (- 0 in the laboratory frame) rotated at 20
to be ignored because does not correspond to resonance
conditions
- for spin precession
precession motion of the spins is now frozen
- spins rotates at the same frequency as the r.f. field and the rotating frame
- this precession motion created by B0 does not exist in the rotating frame
Summary:

In the rotating frame, the nuclei would no longer appear to precess but would become stationary and
coincident with the magnetic field axis B0. The magnetic behaviour is now completely described by a
magnetization vector M0 acting along B0

II,2 Production of pulses

Let us consider a radiofrequency field B1 applied for a very short period
All the nuclei with Larmor frequency i can be excited in a frequency range

a) r.f. pulse sequence with frequency 0 and pulse time tp

along with a repetition time tr of the pulses.
b) Representation of the resulting frequencies.

II,3 The pulse NMR experiments

1) Nuclei are excited during a very short time (pulse duration tp)
2) Radiofreqeuncy pulse with frequency 0 (0 close to the Larmor frequencies of the nuclei
included in the sample studied)
polychromatic wave 0 1/tp.
3) Radiofrequency pulse is stopped
4) Recording of the time signal F(t)
(desexcitation signal de dsexcitation but not absorption signal)
5) Fourier Transform F(t) F()

A conventional pulse NMR experiment

1 2
3

z
Bo app

z
Bo app

Mz = M0

z
Bo app

Bo app

Mx',y' = M0
y'

y'

y'
B1

x'

Entremoments
instants 1 et
2 2
Between
1 and
B1 pulse
along
x-axis
Impulsion
B1the
selon
x'

Instant 2 2
Moment
EndFin
of the
r.f. pulse
impulsion
Magnetization
has
rotated
= 90
Aimantation a bascul deby
=90C

equilibrium
z
Bo app
M

Mx',y'
x'
Instant 4 4
Moment
Mouvement
prcession
Precessiondemotion
Relaxation
Relaxation

Instant 3 3
Moment
Precession
Mouvement
de motion
prcession
Relaxation

Bo app

Mz

i > 0

x'

x'

x'
Instant 01
Moment
Equilibre
de Boltzmann
Maxwell-Boltzmann

y'

Bo app

Mz = M0

Mx',y'
y'

y'
x'

y'
x'

Relaxation
Relaxation

Instant 5 2
Moment
Maxwell-Boltzmann
Equilibre
de Boltzmann
equilibrium

II,3,1 Effect of the r.f. pulse on the macroscopic magnetization

z

M0
During time tp, M has rotated = *B1*tp

- pulse angle
- B1 pulse power
- tp pulse duration

y'
x'

Usually, B1 and tp are chosen to reach = /2 (90)

For instance : proton = 26,75.107 SI, B1 = 6.10-4 T therefore tp = 10 s for = /2

Two main types of pulse

a) High B1 value
- short pulse
- large frequency range centered at 0 (polychromatic, all nuclei will be excited)
- non selctive pulse ( hard pulse )
b) Low B1 value
- long pulse
- narrow frequency range (monochromatic)
- selective pulse ( soft pulse )

y'
x'

B1

II,3,2 Free Induction Decay (F.I.D.) signal

z

The spin system then follows his own evolution in the abscence of B1

M
Mz

Two phenomena :
- free precession around the direction of the field B0 with a frequency 0
Mx',y'

- relaxation (exponential decay)

x'

Magnetization motion M is given by Bloch equations

Mx,y = M0 * exp(- t/T2) * exp (i0t)
T1 : longitudinal or spin-lattice relaxation time
exponential
decay

precession

T2 : transverse or spin-lspin relaxation time

Mz = M0 * (1 - exp(- t/T1))
Cons :

- only the transverse magnetization Mx,y is detected by the receiver coil

- free precession signal decreases with a time constant T2

y'

F.I.D. : different types

synchronous detection 0
a) Spin system such as = 0
F.T.
magnetization remains aligned
along y axis

b) Spin system such as 0

F.T.

c) Real sample: different kinds of nuclei with 1 2 3 0

F.T.
F.I.D. overlap

F.I.D. : different shapes

4 different frequencies

2 different frequencies

1 high frequency

1 low frequency

II,3,3 Signal processing: Fourier Transform

a) Analog signal (voltage)

digital signal

b) Limitations due to memory size which require the F.I.D. truncation, followed by data improvement
c) Fourier Transform
F(t)
F.I.D.
time
signal

The F.T. includes:

F()
frequency
signal

F.I.D.

F(t) = M0 * exp(-t/T2) * cos(2(-0)t)

F.T.

F(
-
0) =

F(t) * exp(2i(-0)t) dt
0

- a real part

absorption spectrum

- an imaginary part

dispersion spectrum

d) Base line and phase corrections, calibration

spectrum

Experimental tips to improve the quality of the final spectrum

a) Phase cycling
Fourier Transform (F.T.) does allow distinguishing positive and negative frequencies
Conventional detection

Detection in quadrature-phase
My

Mx

My

t
t
F.T.

s(t)=My cos t

F.T.

0
sw

sw

s(t)=M0e(it) =My + iMx

sw: spectral width
Cons : Phase cycling provides only positive peaks

b) Zero filling
td: time domain: number of points used to digitize the F.I.D. signal and data are stored
si: size of the file containing the data corresponding to the real part of the F.T. of the F.I.D.
aq: acquisition time
aq = td/(2sw)
digital resolution: sw/si
SI=4K

TD=4k
Conventinal processing
190 150 90 50 10 -30
(ppm)

Zero filling

TD=1k

-90

SI=4K

190 150 110 70 30 -10 -50 -90

(ppm)

F.I.D. Truncation

TD=256

SI=4K

190 150 110 70 30 -10 -50 -90

(ppm)
Cons : Zero filling or F.I.D truncation allows significant enhancement of the signal/noise ratio

c) Filters
lb: line-broadening factor

Without filters

190 150 110 70

30

-10

-50

-90

(ppm)

EM with lb=50Hz

190 150 110 70

30

-10 -50 -90

(ppm)

EM with lb=500Hz

190 150 110 70

30

(ppm)

Cons : Enhancement of the signal to noise ratio by using filters

but to be used with caution to keep a good spectral resolution

-10 -50 -90

II,3,4 NMR spectrum

experiment
exprience 11

Conventional
NMR spectrum

1H

largeur
pulse
impulsion
duration
10 10
s s

temps
acquisition
d'acquisition
time
retard
acquiqition 11ss
d'acquisition
delay
100 s
100 s

N experiments in a short time

experiment
exprience 2

Intervalle time
de relaxation
relaxation
depends
dpend
de
T
et
de
on T1 and values
1
55to 10 s

Sensitivity improvement

signal
noise

Ex : 1H NMR spectrum of butan-2-one recorded in CDCl3

ratio =

II,4 NMR spectrometer

Schematic representation of a Fourier Transform NMR spectrometer

II,5 Relaxation phenomena

Basics:
i) Creation of the permanent magnetization M0 along the z-axis (or B0 axis) at the Maxwell-Boltzmann equilibrium
ii) Radiofrequency pulse B1 inducing the rotation of M0 in the (xy) plane
iii) Relaxation yields the recovery of the permanent magnetization M0 along the z-axis (or B0 axis)

Relaxation ruled by two simultaneous and independent processes:

- Mz recovery along z-axis

T1 relaxation time

- Mxy decay in the (xy) plane

T2 relaxation time

T1: spin-lattice (longitudinal) relaxation, loss of energy from the excited nuclear spins to the surrounding
molecular lattice
T2: spin-spin (transverse) relaxation, loss of energy within the spin system (between excited nuclear spins)
a) Spin-lattice or longitudinal relaxation time
1
Different mechanisms

T1

1
T1DD

dipole-dipole
(dipolar)
relaxation

1
T1SR

1
T1Q

1
T1csa

spin
quadrupolar chemical shift
rotation relaxation
anisotropy
relaxation
relaxation

Cl
1
6

Cl

Ex : Solution 13C NMR: dipole-dipole relaxation

2
3

5
4

Cl

T1

1
T1DD

1H2 * 13C2 * c *

1
RC-H6

1/R6 law therefore less efficient as RC-H increases

Favourable for CH, CH2 and CH3
Unfavourable for Cquat

Order of magnitude:

1H

T1 1 s
T1 from few ms to 102 s

NMR
13C NMR

b) Spin-spin or transverse relaxation time

1/2 =

with

T2*

1
T2*

1
T2

B0
2

spin-spin
static
relaxation
field
time
inhomogeneity

Rem : Heisenberg uncertainty realtions

1
2t

with t = excited state life time

Long life time (stable state)

sharp line

Weak life time

broad line

c) Applications: Magentic Resonance Imaging (MRI)

MRI principle:

Images built from contrast changes induced by the differences in relaxation

time T1 (or T2 ) in biological tissues
Tissue

T1
(s)

T2
(ms)

Muscle

0.75

50

Fats

0.25

85

Blood

350

Values for B0 = 4,7 T

Use of contrast agents to enhance T1 and/or T2 differences

Brain
tumor
Gd-DTPA complex

III Examples
III,1 1H NMR
= 26,752.107 rad.T-1.s-1 The most sensitive and easily observed nucleus

N = 99,985 %,

635.12
631.14
622.30
618.21

693.50

803.62
797.09

876.25
867.74
863.43
854.92

915.17
905.22
903.56
893.50

1092.40
1086.76
1042.76
1039.00
1035.02
1034.13
1030.82
1026.84
1023.30
1022.41
1018.76
1014.78

1146.02
1142.48
1136.07
1132.53

a) 1H NMR spectrum (300 MHz) (solvent CDCl3)

Cl

Cl
Cl H 2 H 1

Cl

H
Cl

H3

Cl

3.8

3.7

3.6

3.5

3.4

3.3

3.2

3.1

3.0

2.9
(ppm)

1.0122

1.0205

1.0200

0.9876

1.0000

H5

2.8

2.7

2.6

2.5

2.4

2.3

2.2

2.1

2.0

Br

b) 1H NMR spectrum (300 MHz) (solvent CDCl3) of cholesterol-5,6-epoxide

HO

7.0

6.5

6.0

5.5

5.0

4.5

4.0

3.5
(ppm)

3.0

2.5

2.0

1.5

1.0

0.5

III,2 19F NMR

= 25,181.107 rad.T-1.s-1 Good receptivity, easily observed

N = 100 %,

a) 19F NMR spectrum (94 MHz) of NaBF4 (solvent D2O)

Overlap of the spectra of 2 isotopologues (or isotopomers)

Na11BF4 + Na10BF4

b) 19F NMR spectrum (188 MHz) of CF3(CF2)7(CH2)2Sn(C6H9)3 (solvent CDCl3)

C4H9
F

F F

F F

F F

F H H

Sn
F

F F

F F

F F

C4H9

F H H
C4H9

III,3 31P NMR

= 10,841.107 rad.T-1.s-1

N = 100 %,
31P

Lower receptivity
Longer acquisition times

NMR spectrum (40 MHz) of a human forearm (in vivo NMR)

Pi : free phosphate ions

PCr : phosphocreatine
, et : 31P nuclei located
at , et positions in
adenosine triphosphate
(ATP)

NH2
N

H
N

O OH
P OH

O
HO

P
OH

HN C
N CH2COOH
H3C
creatine phosphate
phosphocreatine

O
O

P
OH

O
O

P
OH

N
O
H H

H
H
HO OH

adenosine
triphosphate
(ATP)
adenosine
triphosphate
(ATP)

III,4 13C NMR

= 6,7283.107 rad.T-1.s-1

N = 1,108 %,

Low receptivity,
Long accumulation times

Multipulse techniques (dcoupling, INEPT, DEPT), favourable NOE effect

13C-{1H}

NMR spectrum (250 MHz) (solvent : CDCl3) of cholesterol-5,6-epoxide

HO

80

75

70

65

60

55

50

45
(ppm)

40

35

30

25

20

15

10

III,5 119Sn NMR

= -10,021.107 rad.T-1.s-1

N = 8,58 %,

Low receptivity,
Long accumulation times

Multipulse techniques (dcoupling, INEPT, DEPT), additional issues

related to the negative value of the magnetogyric ratio (unfavourable NOE effect)

119Sn-{1H}

R
O
R
O

II

F2Sn

SnF2 + Sn(OR)4
R=

-400

-420

-440

-460

-480

-500

-520

119Sn-{1H}

NMR spectrum

tBu, tAm

-540

-560
(ppm)

-580

NMR spectrum of Cy3Sn(CH2)21CH3

IV

SnOR

O
R

-600

-620

-640

-660

-680

-700

-720

120

80

40

-40

-80

-120

-160
(ppm)

-200

-240

-280

-320

-360

-400

-440