Dr. USAMA El-AYAAN

Nuclear Magnetic
Resonance Spectroscopy
 

Introduction
NMR is the single most widely used
physical technique because its wide
application.
It is used to study a wide variety of nuclei:
1H
13C
15N
19F
31P

   !    $ %  

  . I &' '&  ($ quantum numbers

 0& 1& .('+  ,-.(&  &   *   78  5+ 12* 
* ,-.(*   56$ 1H 12
.tiny magnet '(+ *,-.(& 96: 5+

spin

Dr. USAMA El-AYAAN

The NMR Spectrometer

Dr. USAMA El-AYAAN

=>

Nuclear Spin
.  ) ( ' %&'  #   
.0'12    +# -  /  

A nucleus with an odd atomic number or an odd mass number has a nuclear spin.
The spinning charged nucleus generates a magnetic field.

=>
Dr. USAMA El-AYAAN

External Magnetic Field

)9 %: ;% / 9   #(6 4) 4  < =? 4
When placed in an external field, spinning protons act like bar magnets.

Dr. USAMA El-AYAAN

Two Energy States

  A44NMR ): 0;
/  6 C) B
.0'12  DEF
E E
HF G4  0J4 (  / %9)
%    4E

Dr. USAMA El-AYAAN
Dr. USAMA El-AYAAN

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8

E and Magnet Strength

Energy difference is proportional to the
magnetic field strength.
E = h = h B0
Strength of the applied mag. filed
2

Gyromagnetic ratio, , is a constant for each

nucleus (26,753 s-1gauss-1 for H).
In a 14,092 gauss field, a 60 MHz photon is
required to flip a proton.
Low energy, radio frequency.
Dr. USAMA El-AYAAN

Magnetic Shielding
If all protons absorbed the same amount of
energy in a given magnetic field, not much
information could be obtained.
But protons are surrounded by electrons
that shield them from the external field.
Circulating electrons create an induced
magnetic field that opposes the external
magnetic field.
Dr. USAMA El-AYAAN

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Magnetic Shielding
K9 DEF / (= - HF  (= 4E 0 L?
.NMR 
H  M' 6H 4
.%:O / - )E/4 %' N2  4E

% / - P1  B 'Q

.%:O /'= -

Dr. USAMA El-AYAAN

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Shielded Protons
/  4E B %9 H - ( %&-) / R SBK
 - W &  C # ? Q  %' ( %&-)
. 2 / 4E
Magnetic field strength must be increased for a shielded proton to flip at the same frequency.

Dr. USAMA El-AYAAN

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Protons in a Molecule
Depending on their chemical
environment, protons in a molecule
are shielded by different amounts.

Dr. USAMA El-AYAAN

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=>

NMR(4 - &Y

62 Z
NMR signal

The number of signals shows how many

different kinds of protons are present.
The location of the signals shows how
shielded or deshielded the proton is.
The intensity of the signal shows the number
of protons of that type.
Signal splitting shows the number of protons
on adjacent atoms.
=>
Dr. USAMA El-AYAAN

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NMR(4 - &Y

62 Z

     signals -1

#$*, #$% &' ( * +% signal "-2

'0  
   signal / -3
$ 3 
     signal splitting -4

Dr. USAMA El-AYAAN

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Deshielding

Shielding
A/B %&-

 E/B 0H

Dr. USAMA El-AYAAN

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CH3
H3C

Si CH3
CH3

TMS is added to the sample.

Since silicon is less electronegative
than carbon, TMS protons are highly
shielded. Signal defined as zero.
Organic protons absorb downfield (to
the left) of the TMS signal.
Dr. USAMA El-AYAAN

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Chemical Shift
Measured in parts per million.
Ratio of shift downfield from TMS (Hz) to
total spectrometer frequency (Hz).
Same value for 60, 100, or 300 MHz
machine.
Called the delta scale.

Dr. USAMA El-AYAAN

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 @' A- CD E:* '! &CD F TMS >=

.1H NMR *5C F
G EH& . !* 5
=
reference compound
tetramethylsilane
TMS

CH3
CH3 Si CH3

:I> F0& E
 @KL *
M 7  '
.9(!*

CH3
Highly shielded
protons appear
way upfield.

TMS
shift in Hz
downfield

Dr. USAMA El-AYAAN

Chemists originally
thought no other
compound would
come at a higher
field than TMS.
19

h F; 6H 9 %F; 6: K 0M 62  O4 
:NMR h 0&4 -  ^  YC: %9 (&O  4E
. Z 0 ; A K
0M 62 .1
26.5 oC ^(O  _&: ` F 0Z
.2
. C ` G&O 0) # 26.
/  %&-( B %( eO) f #) B % / H - ): G4 `4 42 .3
J %&- (<  J TMS %FO hF #;P .0& 6 & (F FO
. (ppm)  & C/2 )- E %

4 Hz C4)2 )- E  4E BQ H

)/'&  9 .J %9 O) / 4 H %&.%&- B %&- 0? %- 4

E& C4) O
 - &'1
: 4E& C  Higher frequencies
= larger shifts in Hz.

TMS
shift in Hz
downfield
20

Dr. USAMA El-AYAAN

F H 2 4n `2o H () Z' BQ

The shifts from TMS in Hz are bigger in higher field:
instruments (500 MHz > 400 MHz > 300 MHz > 200 MHz )

We can adjust the shift to a field-independent value,

the chemical shift in the following way:

chemical
=
shift

parts per
million

shift in Hz
= ppm
=
spectrometer frequency in MHz

This division gives a number independent

of the instrument used.

O
F H 4 6 H =( - )f & A %9  42
Dr. USAMA El-AYAAN

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Delta Scale

Dr. USAMA El-AYAAN

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=>

Location of Signals
More electronegative
atoms deshield more and
give larger shift values.
Effect decreases with
distance.
Additional
electronegative atoms
cause increase in chemical
shift.
Dr. USAMA El-AYAAN

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 ?Q CB 6H %&- oq 0 



/2 oP   A/2  AE  B 'Q 9M'

- )f  h 0/ ` PR  #( shielding) %:O %
.%- % /
/2 oP   A/BK2  AE  B 'Q 9M' GJ

/ - )f  h 0/  (deshielding) %:O %
.W(O %
downfield (deshielding) = left side of spectrum

upfield (shielding) = right side of spectrum

delta values increase from right to left!

A H oP4 r  :M
most
deshielded

24

CHCl3 CH2Cl2 CH3Cl

7.27 5.30
3.05 ppm
Dr. USAMA El-AYAAN

Typical Values

Dr. USAMA El-AYAAN

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13C
12C

is not NMRNMR-active

however.

13C

NMR h
I= 0

does have spin, I = 1/2 (odd mass)

:AE2 1H NMR (F RQ  h 13C NMR (F RQ

%100) : ): 4 E2 J (1.08%) EF %9 13- 2' : E (O .1
.( EJ4
vB .:  )% C2 J 0&H 13- 2'  % C .2
  B %9 `H 62 13- 2'  E2 :Gyromagnetic constant L2M
.:)

# 1H NMR hF2 J M'2    H #;P 13C NMR h 0/4 #

.(JH 2-1) : 0&H  %9 &/4 w
1H

NMR B %9 ` E 13C NMR %9 Z' BQ 

Dr. USAMA El-AYAAN

0 - 220 26ppm

Typical 13C

13C

NMR h

NMR

the wave function for the

highest
occupied
molecular
orbital
for
Carbon 60

Dr. Richard Smalley

Dr. USAMA El-AYAAN

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Fax
Feq
Feq

Feq
Feq

IF5 has a square-pyramidal geometry,

with one axial fluorine and four
equitorial
fluorines.
Coupling
between the inequivalent fluorines
should give rise to a quintet for the Fax
resonance and a doublet for the Feq
resonance

Feq doublet
Fax quintet

Dr. USAMA El-AYAAN

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Brisdon, p. 34

31P

NMR Spectroscopy

As with 19F NMR spectroscopy, 31P NMR spectroscopy is a fairly routine

experiment for phosphines
phosphines,, phosphites
phosphites,, phosphine oxides, phosphates,
and other phosphorus containing compounds, as it is 100%
100% abundant.
The chemical shift is sensitive to the oxidation state (P(III) vs P(V)) and
the nature of the groups attached to the P atom.

Compound
PMe3
PEt3
PBu3
PPh3
[PEt4]+
[PF6]-

(ppm)
-62
-20
-33
-7
+40
-145

Compound
Me3PO
Et3PO
Bu3PO
Ph3PO
P(OMe)3
P(OEt)3

Dr. USAMA El-AYAAN

(ppm)
+36
+48
+43
+29
+140
+138

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31P

NMR for metal phosphine complexes

Cl

R3P
R3P

Cl
Cl

R3P

M
Cl

R3P

PR3

fac-[M(PR3)3Cl3]
All three PR3 ligands are in
the same chemical
environment, so the 31P
NMR spectrum would have
only one resonance

Cl
M
Cl

PR3

mer-[M(PR3)3Cl3]
There are two PR3 ligands are in
the same chemical environment
(trans to each other) and the other
in a different environment, so the
31P NMR spectrum would have two
resonances, with a 2:1 relative
integration

Dr. USAMA El-AYAAN

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31P

NMR for metal phosphine complexes

Cl

R3P
R3P

Cl
Cl

R3P

M
Cl

R3P

PR3

fac-[M(PR3)3Cl3]
All three PR3 ligands are in
the same chemical
environment, so the 31P
NMR spectrum would have
only one resonance

Cl
M
Cl

PR3

mer-[M(PR3)3Cl3]
There are two PR3 ligands are in
the same chemical environment
(trans to each other) and the other
in a different environment, so the
31P NMR spectrum would have two
resonances, with a 2:1 relative
integration

Dr. USAMA El-AYAAN

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19F

and 31P NMR spectra of the PF6- ion

F
F

F
P

F
F

In the octahedral PF6- ion, all six fluorine

nuclei are identical.
The 19F NMR spectrum would be expected
to show coupling of the six equivalent F
nuclei to one P nucleus to give a doublet
for the F resonance
The 31P NMR spectrum would be expected
to show coupling of the P nucleus to 6 F
nuclei, giving a regular septet for the P
resonance.

Dr. USAMA El-AYAAN

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Coupling
Consider one H split by one F

Dr. USAMA El-AYAAN

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Brisdon, p. 36

Coupling
I = 1/2

Dr. USAMA El-AYAAN

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Brisdon, p. 37

Coupling
I = 1/2

Dr. USAMA El-AYAAN

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Brisdon, p. 38

Si(OCH2CH3)2
J = ((4
4.377377- 4.342
342))ppm x 200 MHz = 7 Hz

Dr. USAMA El-AYAAN

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19F

and 31P NMR spectra of the PF6- ion

1J
PF

= 709 Hz (typical range is 500-1500 Hz

septet

doublet

Dr. USAMA El-AYAAN

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Brisdon, p. 38

31P

NMR
spectrum

1J (axial)
PF

A doublet of
triplets
1J (equitorial)
PF

19F

NMR
spectrum

Dr. USAMA El-AYAAN

Iggo, NMR Spectroscopy in Inorganic Chemistry, p. 38-40

38

31P

NMR spectrum of [Rh(PPh3)3Cl]

Wilkinsons Catalyst (Rh

Rh(PPh
(PPh3)3Cl) has three PPh3 ligands in
two different chemical environments (cis and trans to the Clligand)). In addition to the two sets of P nuclei coupling to
ligand
).
each other, they are also coupled to 103Rh (I = ).

Dr. USAMA El-AYAAN

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Iggo, NMR Spectroscopy in Inorganic Chemistry, p. 36

Dr. USAMA El-AYAAN

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