Applications of 1H, 13C, 19F and 31P - NMR

spectroscopy in the structural assessment of

inorganic compounds
 Establishing the number and connectivity of
NMR Spectroscopy
certain atoms in a molecule

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 Theory

NMR is possible owing to the magnetic properties of certain nuclei. In addition

to charge and mass, which all nuclei have, various nuclei also possess a
property called nuclear spin, which means that they behave as if they were
spinning. Since nuclei have a charge, they generate a magnetic field with an
associated magnetic moment.
There are useful empirical rules relating mass number, atomic number (Z) and
nuclear spin quantum number (I):

Mass Z I Example
Number
even even 0 O8
16

odd Even or odd 1/2, 3/2, 5/2 C6, 11B5

13

even odd 1,2,3 N7

14

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NMR depends on the existence of a nuclear spin (I)
 
Nuclei with I = 0 (I is the nuclear spin quantum number) have no NMR spectrum
(12C, 16O, 18O).
 
From standpoint of generating NMR spectra, the most important class of nuclei are
those with I = 1/2.
1
H (natural abundance 100%), 13C (natural abundance 1.108 %),
15
N (natural abundance 0.365%), 19F (natural abundance 100%),
29
Si (natural abundance 4.71%), 31P (natural abundance 100%),
57
Fe (natural abundance 2.17%), 195Pt (natural abundance 33.8 %).
 
Nuclei with I  ½ (11B, I = 3/2; 14N, I = 1) have quadrupole moments, a non-spherical
distribution of nuclear charge, which results in broad absorption lines and make
observation of spectra more difficult.

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 In NMR experiment, the sample is placed in a strong magnetic field, B0.

Since the spin of the magnetic nuclei are quantized, they can have only certain well-
defined values. If we have nuclei with I = ½ (e.g. 1H, 13C, 19F, 31P) the spins can orient
only in two directions: either with (mI = +1/2, ) or against (mI = -1/2, ) the applied
field. NMR transitions are allowed for cases where mI = 1.

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 +

There is an energy difference, E, between two states, and is given by

E = h = (h/2)  B0
 = (1/2)  B0
Where, h is the Plank’s constant,  is the gyromagnetic ratio ( = 2/hI, where 
is the magnetic moment of the nucleus) and B0 is the applied magnetic field.

When the energy of the incoming radiation matches (is in resonance with) the
energy difference between the spin states, energy is absorbed and the nucleus
is promoted from the lower +1/2 to the higher -1/2 spin state.
NMR transitions occur in the radio frequency range of the electromagnetic
spectrum.

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 E = h = (h/2) B0
+
E depends only on  and B0.

The gyromagnetic ratio, , is an intrinsic property of the magnetic nucleus.

Therefore, each type of nucleus has a distinct and characteristic value of .

E is directly proportional to B0, the external magnetic field.

The higher the external field, the greater is the energy separation between the 
and  spin states. Or we can say the resonance frequency of the nucleus increases
with increasing B0.

B0 (tesla) Resonance frequency (, MHz)

H
1 13
C 19
F 31
P
2.35 100 25.2 94.1 40.5
4.70 200 50.4 188.2 81.0

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 Chemical Shift

The frequency of the NMR absorptions of a given nucleus also depends on the
chemical environment of the nucleus. The variation of the resonance frequency
with chemical environment is termed the chemical shift.

The actual field (Beff) felt by a nucleus is thus less than B0, and the ability of the
electrons to alter the field at the nucleus can be expressed by , the shielding
constant.
Beff = B0(1-) or ,

or, eff = (1/2)B0(1-)

Nuclei are said to be shielded or de-shielded depending on the presence or

absence of electron density surrounding them.

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 Chemical shift () are expressed in units of parts per million (ppm) of the
spectrometer frequency with respect to a reference material whose position is
arbitrarily assigned a value of 0.0 ppm.

When expressed in such dimensionless unit ( in ppm), the chemical shift are
invariant of the frequency of the spectrometer and can be used as molecular
parameters.

If the same sample is run at two different spectrometer frequencies, the chemical
shift of the resonances will be identical
[ = 60Hz/60 MHz = 1 ppm;  = 200Hz/200MHz = 1ppm].
Naturally, this statement is only true if the same reference material is used for
each spectrum.

Different references are used for different nuclei.

The most widely accepted reference for 1H and 13C NMR is tetramethylsilane (TMS =
Si(CH3)4), for 19F NMR is CFCl3 and for 31P NMR spectroscopy is 85% H3PO4.
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Integration

The area under each NMR absorption peak can be electronically integrated to
determine the relative number of nuclei responsible for each peak. The integral of
each peak can be provided numerically, and is often accompanied by a line that
represents the integration graphically.
1
H-NMR spectra of CH3OC(CH3)3

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 Spin-spin splitting (Coupling) and Coupling Constant

The spin-spin coupling is caused by magnetic interaction of the chemically non-

equivalent nuclei via the bonding electrons and NMR peaks are split into
multiplates.
The separation between the two peaks is called the coupling constant, J, which is
expressed in Hz.

Spin-spin coupling has the following characteristics:

1. The magnitude of J measures how strongly the nuclear spins interact with
each other.
2. Coupling is normally a through bond interaction, and is proportional to the
product of the gyromagnetic ratios of the coupled nuclei.
1
JCH = 124 HZ in CH4, 1JSnH = 1931 Hz in SnH4. ( of 119Sn  13C)

3. Since coupling occurs through chemical bonds, the magnitude of J normally

falls off rapidly as the intervening bonds increases. E.g. 1JPH 700 Hz; 2JPH  20 Hz.

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 4. Since spin-spin coupling is a through-bond interaction, it is sensitive to the
orientation of the bonds between two interacting nuclei. This is particularly
important for two-bond coupling constant.

, in this case 2JHaHb  3JHaHc  3JHbHc

5. Spin-spin interactions are independent of the strength of the applied field. The
spacing between lines at two different field strength will be the same if it is due to
coupling, but will be proportional to the field strength if it is due to a difference in
chemical shift.

6. One nucleus is split by (n) equivalent nuclei into (n+1) peaks, each separated by
the coupling constant x J AB. The number of peaks is referred to as the multiplet.

7. The number of lines (N) in the multiplet due to the spin-spin coupling is given by
N = 2nI + 1 (where I = Nuclear spin quantum number, n = number of neighbouring
magnetically equivalent nuclei)

8. Intensity pattern of the multiplet can be determined using Pascal’s triangle.

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Pascal’s triangle predicts the number of peaks in a multiplet and their relative intensities.
 

The splitting tree of different types of multiplets.

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 Analyzing NMR spectra and reporting results

 1H –NMR spectral data of B(OCH2CH2)3N obtained in a 200 MHz spectrometer. Find out
the coupling constant J (Hz).

3
JHH = [ (3.914-2.857)/2}  (200
106 Hz)] / 106
= { (3.914-2.857)/2}  200 Hz
= 5.7 Hz

Chemical shift,  (ppm) Multiplicity Integration Assignm

ent
3.05 (3.078, 3.049, 3.021) triplet 10.2 units = 2H NCH2
08/31/20203.89 (3.914, 3.886, 2.857) triplet 10.0 units = 2H OCH2 14
 Acetylacetone (2,4-pentanedione) is an organic compound, a β-diketone, that
exists as an equilibrium mixture of tautomeric keto and enol forms. In basic
solution, it is deprotonated to form the acetylacetonate anion (acac).

Keto-enol equilibrium of acetylacetone and

formation of acetylacetonate anion

The acac anion can act as a ligand towards metal ions, typically forming a bidentate
complex where the metal is bound to the two oxygen atoms, thus forming a 6-
membered ring. Metal acac compounds are typically isolated as crystalline solids that
are neutral, hence an Mn+ metal forms a complex with n acac ligands

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1
H NMR spectrum of acetylacetone in CDCl3. 

CH3 of enol form

Keto form
CH CH3
CH2
of enol form
OH

The resonances belonging to the keto form are those at 3.46 (CH2) and 2.07 (CH3) ppm,
and enol form are those of 1.88 (CH3) , 5.37 (CH) and 15.41 (OH) ppm

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 With the resonance in the spectrum assigned to each tautomer,
the keto-enol ratio can be calculated.

The CH of the enol tautomer and CH2 of the keto tautomer are well separated ,
Therefore, their integrals can be used to determine the ratio.
Integrate the peaks at  = 5.37 (peak area 1.00) and  = 3.46 ppm (peak area
0.36) and divide the keto integral by two, the number of protons it accounts for
the molecule.
The keto resonance has an integral of 0.36, thus normalizing to correspond this
to concentration (dividing by two) gives 0.18.

Therefore, the keto: enol ratio is about 1: 6 in CDCl3.

[keto/enol= 0.18/1.00 = 1/6]

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 1
H-NMR spectrum of [Al(acac)3] in CDCl3

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 1
H-NMR spectrum of [CoIII(acac)3] in CDCl3

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 Compound -CH ( ppm) -CH3 ( ppm)
acac (enol form) 5.37 1.88
[Al(acac)3] 5.47 1.99
[Co(acac)3] 5.52 2.18

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 H-NMR spectrum of [Mn(acac)3] in CDCl3
1

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 1
H-NMR spectrum of the reference
sample (10% t-butanol) and the
reference with
Mn(acac)3 overlaid. The peaks are
labelled in Hz.

Where Xm is the molar susceptibility of the solute

(m3 mol-1), c is the concentration of the substance
(mol dm-3), Δf is the observed shift in the frequency
of the reference compound (Hz) and f is the
frequency of the spectrometer (Hz).
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 Molar susceptibility:
[Mn(acac)3] = 0.028 mol dm-3

Δf = 57.87 – 37.76 = 20.11 Hz

 
f = 42,500,000 Hz
Using Equation 1 ,

Xm = 1.00 x 10-7 m3 mol-1.

 
Effective magnetic moment:
The molar susceptibility calculated above is used to determine the effective
magnetic moment according to Equation
T = 294.16 K
Using Equation 2, μeff = 4.33 BM.

The high spin complex has four unpaired electrons and the low spin complex has two.
Use Equation μeff = n(n+2) to estimate the expected effective magnetic moment for
each electronic structure.
High spin, n = 4 ; μeff = 4.90 BM
Low spin, n = 2 ; μeff = 2.83 BM
The magnetic moment of the high spin complex is much closer to the experimental
value, therefore it can be determined that the complex is high spin.
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 1
H-NMR spectra of [FeIII(acac)3] in CDCl3

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 We can get the following information from a 1H Nuclear Magnetic Resonance (NMR)
structure:

The number of signals gives the number of non-equivalent hydrogens

Chemical shifts show differences in the hydrogens’ chemical environments

Splitting presents the number of neighboring hydrogens (N+1 rule)

Integration gives the relative number of hydrogens present at each signal

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