Short Notes on Application of NMR Techniques to Inorganic Molecules

Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,
1


The Chemical Shift
An isolated nucleus such as hydrogen nucleus has a precessional frequency of 100
MHz at field strength of 2.3487 T. But all nuclei are associated with electrons, which revolve
around them. As a charged particle in circular motion, the electrons also produce a magnetic
moment, and this is called as secondary or induced magnetic field.
When placed in an applied magnetic field, the induced magnetic field of the electrons
may oppose the net magnetic field experienced by the nucleus i.e., the electrons may circulate
in such a way its magnetic field is opposing the applied field. This circulation is known as
diamagnetic circulation. In diamagnetic circulation the electrons and the nucleus are spinning
in opposite direction to each other. On the other hand if both are spinning in the same
direction the circulation may be paramagnetic one.
Thus the nucleus can be shielded from the applied field by diamagnetic circulation of
electrons. The extent of shielding will be constant for a given atom in an isolated condition,
but will vary with the electron density about an atom in a molecule. The above equation may
be generalized as
B
i
= B
0
(1- σ
i
) where B
i
is the net magnetic field felt by a particular nucleus ―i‖ its shielding
constant is σ
i
For example we know that oxygen atom is more electro negative than carbon
and hence the electron density about the H atom in C-H bonds should be considerably higher
than that in O-H bonds.
We can expect σ
CH
> σ
OH
and hence
B
CH
= B
0
(1- σ
CH
) < B
OH
= B
0
(1- σ
OH
)
i.e., the C-H protons are highly shielded and felt less applied field. But, the O-H protons are
less shielded and felt more applied field. Due to this reason the C-H proton precess with a
smaller Larmor frequency than that of O-H proton.
Thus in order to come
into resonance with a radiation
of particular frequency
(~100MHz at a field strength
of 2.3487T), a C-H proton
requires a greater applied field
than the O-H proton. For
example when we record the
1
H N.M.R. spectrum for
methanol we can see that the
O-H proton will give the signal
first i.e., at comparatively
lower field than the C-H
proton. The C-H proton signal is obtained at higher field to that of O-H proton.
Short Notes on Application of NMR Techniques to Inorganic Molecules

Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,
2


In N.M.R. spectrum thus the identical nuclei can give rise to different absorption
positions when present in different chemical surroundings as in the case of methyl and
alcohol protons in methanol. The separation between absorption peaks is usually referred to
as chemical shift.
Internal Standard
For the measurement of chemical shift we have to take tetramethylsilane, Si(CH
3
)
4

(TMS) as an internal standard. With reference to the signal of TMS we have to find out the
shift in the position of other signals.
Since TMS is immiscible with water for aqueous samples we may use
(CH
3
)
3
SiCH
2
CH
2
CH
2
SO
3
Na as an internal standard. For
13
C spectrum also these two
substances may be used as a reference. The advantages of TMS are
1. Its resonance is sharp and intense since all 12 H nuclei are equivalent and hence absorb at
same position.
2. The resonance position of TMS is too high field of almost all other H absorptions in
organic molecules and hence can be easily recognized.
3. It is a low boiling liquid (b.P.27
o
C) and so can be readily removed from the most samples
after use.
Conventionally N.M.R. spectra are displayed with the field increasing from the left,
which places TMS signal to the extreme right. Two measurement scales are used, o scale and
t scale. In t scale, the TMS signal is marked as 10p.p.m. and the chemical shift value is
decreasing towards left. In o scale the TMS signal is marked as 0p.p.m. and the chemical shift
value is increasing towards left. The relationship of these two scale is o =10 - t.
The Coupling Constant
Generally the peaks of proton N.M.R. spectrum are splitting into two or more & the
distance between the adjacent peaks in a multiplet is known as coupling constant. The reason
for this is the spin interaction between the two protons when they are present very close
proximity to each other. There are several kinds of spin interactions. When compared to
gaseous molecules the spin-spin interaction will be more in solid substances and takes place
to a smaller extent in liquid molecules.
Factors Influencing Coupling Constant, J Values
1. Geminal Coupling
The protons connected to the same atom are separated only by 2 chemical bonds are
known as geminal protons. The geminal coupling constant values varies from +5Hz to -30Hz
depending on the bond angles between these 2 protons.
2. Vicinal Coupling
The protons present on the adjacent atoms are separated by 3 chemical bonds are
known as vicinal protons. Usually the vicinal coupling constant values vary from 0 to 9 Hz
depends on the dihedral angle. When the dihedral angle, u increases from 0 to 90 the J value
decreases from 9 to 0 and again it increases if the u value rises from 90 to 180. Karplus
equation given below helps to calculate the vicinal coupling constant, if u value is provided.
J = 8.5 cos
2
u - 0.28 (if u = 0 – 90
o
)
J = 9.5 cos
2
u - 0.28 (if u = 90 – 180
o
)

Short Notes on Application of NMR Techniques to Inorganic Molecules

Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,
3


3. Long Range Coupling
If protons are separated by more than 3 chemical bonds the J value is very small.

13
C NMR Spectra
For a
13
C nucleus, the value of I = ½ and has a precessional frequency of 20 MHz in
an external magnetic field strength of 1.9 tesla. But at the same magnetic field strength the
precessional frequency of proton is 80 MHz. Hence the magnetic moment of
13
C nucleus is
1/4
th
the magnetic moment of H nucleus. At the same time the natural abundance of
13
C
nucleus is 1.1% only. So, the NMR signal of
13
C nucleus is very weak.
The problem of weak signal in simple molecules can be overcome by synthesizing
13
C
enriched samples. But this is very difficult in complex molecules. In practice by using pulsed
FT method
13
C NMR spectra are recorded with natural abundance of
13
C, with the sensitivity
enhanced by summation of several spectra.
Chemical shift values vary from 0 to 200 ppm. As both
13
C and H nucleus have I = ½,
we can expect
13
C -
13
C and
13
C –
1
H couplings. The probability of 2
13
C atoms being
together in the same molecule is very low and so
13
C -
13
C coupling is not usually observed.
Due to
13
C –
1
H coupling, the
13
C spectrum will be more complex. This can be
avoided by proton decoupling. The
1
H nucleus can be decoupled by double irradiation at its
resonance frequency (80 MHz at 1.9 T). This is an example of hetero nuclear decoupling. The
following table gives the chemical shift values of some carbon atoms.
Type of C atoms Chemical Shift (o) ppm
sp
3
carbon 0 – 80
sp
2
carbon 80 – 150
sp carbon 70 – 90
sp
2
(aromatic) 110 – 140
C – X 10 – 80
Alcoholic, ether, C – O 40 – 80
C – N 20 – 80
C = O 180 - 200
Here also internal standard is tetra methyl silane (TMS)

19
F and
31
P NMR
The abundance of
19
F is 100 % and its value of I = ½. Its precessional frequency is
56.46 MHz at 1.4 tesla. Internal standard is CFCl
3
or CF
3
COOH and o value varies from 0 to
240 ppm. Geminal F – F coupling ranges from 43 – 370 Hz and vicinal coupling varies from
0 to 39 Hz. Coupling between
1
H –
19
F also strong with geminal coupling value between 42 –
80 Hz and vicinal coupling varies between 1.2 – 29 Hz.
31
P nucleus also has I = ½ with e = 24.3 MHz at 1.4 T. For example, (CH
3
)
2
PCF
2
CH
3

has 84 lines. First the signal of P split into 3 by 2 F atoms, then each line into 4 by single CH
3

protons. Finally each of 12 lines into 7 by 2 CH
3
protons.



Short Notes on Application of NMR Techniques to Inorganic Molecules

Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,
4


Problems
1. HPF
2
: The
31
Pnmr spectrum shows a sextet (three doublets). The two F atoms first split the
phosphorous signal into a triplet and then the H atom split each peak into a doublet. Two
triplets may result if it were J
P
.
H
> J
P
.
F
(When there are two interacting magnetic nuclei
nearby a sample nucleus the nucleus with larger coupling constant value will first cause the
splitting of the signal of the sample nucleus followed by the other nucleus).
When J
P-F
> J
P-H
three doublets

When J
P-H
> J
P-F
Two triplets

Splitting due to one H atom splitting due to two F atoms

2. Protons attached to metal ions are very highly shielded, the peaks often occurring 5 to 1 5
ppm on the high field side of TMS. It is due to non-polar nature of M-H bond. The H nmr of
HRh(CN)
5
3-
is a doublet (I
Rh
= 1/2) which occurs at 10.6 ppm on the high field side of TMS.
3. The
31
Pnmr of Phosphorous acid, HPO(OH)
2
is a doublet and that of Hypophosphorous
acid, H
2
PO(OH) is a triplet. Therefore, the structures are as given below. There is no
coupling due to -OH proton as they are far removed.
P
O H
OH
O
H
P
OH
O
H
H

4. The
31
Pnmr of P
4
S
3
shows two peaks with 3:1 ratio. The more intense peak is a doublet and
the less intense peak is a quartet. S does not couple as I
S
= 0. This spectrum indicates that
there are three equivalent and one unique P atoms.
S
P
P
S
P
S
P

Short Notes on Application of NMR Techniques to Inorganic Molecules

Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,
5


5. Solutions of 1:1 TiF
6
2-
and TiF
4
in ethanol give
19
Fnmr consisting of two peaks with
intensity ratio 4:1 (I
Ti
48
= 0). The low intensity peak is a pentet and the high intensity peak is
a doublet. Therefore the structure is [TiF
5
(OHC
2
H
5
)].
6. Ammonia dissolved in water undergoes very fast proton exchange with water. The NMR
spectrum consists of only one peak, which is the average resonance frequency of all the
protons on nitrogen and oxygen.
7. The
l9
Fnmr spectrum of TiF
4
in donor solvents at —30
o
C consists of two triplets of equal
intensity. This corresponds to the cis-structure. However, the spectrum at 0
o
C shows a single
fluorine peak. This may correspond to the trans structure. But actually the change in the
spectrum at higher temperature is not due to cis - trans conversion but it is due to the
dissociation reaction of type: TiF
4
.2B → TiF
4
.B + B


At high temperature, this dissociation is fast enough as to make all the four fluorine atoms
equivalent.
8. Nuclear quadrupole relaxation changes the splitting pattern. When the relaxation is rapid
the spin state of the nucleus is rapidly changed and as a result splittings do not occur. Slow
relaxation rates cause normal splittings. Intermediate exchange rates often result in a
broadening of the peaks. Relaxation effects are often encountered for nuclei, which have
quadrupole moment because these nuclei are very efficiently relaxed by the fluctuating
electric field gradients, which arise from the thermal motion of the polar solvent and solute
molecules. For N
14
H
3
(I=1), three broad HNMR signals are obtained and forN
15
H
3
(I=1/2; no
quadrupole relaxation), a sharp doublet is obtained.
9. Spin-spin coupling depends also on the number of intervening bonds. In saturated
molecules of light elements J
H
_
H
falls off rapidly as the number of bonds between the two
interacting nuclei increases and usually is negligible for coupling of nuclei separated by more
than three bonds.
10. Long-range couplings are observed in unsaturated compounds. Here the spin-spin
coupling is transmitted through t-bonds, which are delocalized over the entire molecule.
11. Long-range coupling occurs through space instead of t or o bonds in cases where
coupling involves an atom other than hydrogen. For the compound SF
5
.CF
2
CF
3
, J
F-F
(of the
CF2 group and trans- F) is -5 cps while J
F
_
F
(of CF
2
group and the cis-F) is -16 cps. In the
latter case there is through-space coupling.
Short Notes on Application of NMR Techniques to Inorganic Molecules

Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,
6



12. F
19
nmr of CH
2
=CF
2
shows four lines of equal intensity. The two F and two H atoms are
non - equivalent. The two fluorines have the same chemical shift. This peak is split by the
TWO H – ATOMS one by one into four lines of equal intensity (it is not 1:2:1 as If the 2F or 2H
were equivalent).
C C
H
a
H
b
F
a
F
b
cis H-F coupling
trans H-F coupling

13. C1F
3
: Two fluorines are of one type and one F is of other type. The F
19
nmr shows a (1F,
triplet) and a (2F, doublet).
Cl
F
F F

(14) P
4
O
13
6-
: Two peaks viz., (2P, triplet) and (2P, triplet).
(15) P
4
S
3
: Two peaks viz., (3P, doublet) and (1P, quartet)
16. If the molecules being studied are undergoing very rapid exchange reactions, the nmr
spectrum drastically affected. A mixture of CH
3
COOH and H
2
O does not show two separate
O-H resonances from water and acid but instead shows only one. The -OH protons are
exchanging positions very rapidly between the acid and the water.

17. In N.N-dimethylacetamide, the methyl groups a,b,c are non-equivalent at room
temperature as the double bond character of C-N bond restricts the rotation about C-N axis.
As a result, the methyl groups b and a are cis and trans to O-atom and give rise to two peaks.
At high temperatures, rotation becomes free and as a result there is no distinction between cis
and trans methyl groups. Hence, b and c give single peak.
Short Notes on Application of NMR Techniques to Inorganic Molecules

Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,
7



18. NMR spectrum of methylammonium chloride in water at pH = I shows
(i) a quartet methyl peak (split by three NH
3
protons); (ii) a sharp water peak; (iii)
three broad peaks from NH
3
protons (I
N
=1). Broadening is due to quadrupole nature of
Nitrogen. No fine structure due to –CH
3
protons is observed because of quadrupole
broadening by nitrogen.
When pH is increased, all bands begin to broaden. At pH = 5, the spectrum shows:
(i) one sharp peak due to –CH
3
; and (ii) a broad peak due to all other protons.
19. B
3
H
8
-
: B
11
nmr spectrum is a nonet which results from a splitting of three equivalent
borons by eight equivalent protons. Because of the fast intramolecular hydrogen exchange all
B and all H become equivalent.

20. P
3
N
3
Cl
4
F
2
: The
19
Fnmr spectrum shows it is a AB
2
X
2
system. The two F atoms are X
2
,
the P atom to which the fluorines are attached is A and the other two P atoms are B
2
; 1.1-
difluoride-3.3.5,5-tetrachloride.
P
N
N
P
P
N
Cl
Cl
Cl
Cl
F F

21. P
4
N
4
Cl
6
(NHC
6
H
5
)
2
: 31Pnmr shows two triplets of equal intensity. The structure is given
below.
P
N
N
P
N
P
P
N
Cl
Cl
Cl
Cl
Cl
Cl
NHC
6
H
5
H
5
C
6
HN

Short Notes on Application of NMR Techniques to Inorganic Molecules

Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,
8


22. NF
3
: The F
l9
nmr shows a sharp singlet at -205
o
C. As the temperature is raised the peak
broadens and at 20 °C, a sharp triplet (I
N
14
= 1) is obtained. This change is opposite to that
normally obtained for exchange processes. At lower temperatures, the slow molecular
motions are most effective for quadrupole relaxation of N
14
. At higher temperature, the
relaxation is not as effective and the life-time of a given state for N
14
nucleus is sufficient to
cause spin-spin splitting.
23. The N
14
nmr of azoxybenzene exhibits only a singlet. The field gradient at the N-O
nitrogen is so large as to make this resonance unobservable. Only the other nitrogen shows
the signal.
N
+
N
O
-


24.
31
Pnmr spectrum of PF
2
H(
I5
NH
2
)
2
shows 90 lines as explained below.
P
F
F
H
NH
2
NH
2

One P
31
signal gets split into a doublet by one H
Each line in the doublet is split into a triple by two F's (2 X 3 = 6 lines)
Each of these six lines is split into triplet by two 15N’s (I
N
15
= ½) (6 X 3 = 18 lines)
Each of these 18 lines is split into a quintet by the four NH
2
protons (18 X 5 = 90 lines)
25. The proton noise decoupled P
31
spectrum of a mixture of trans - [PtCl
4
(PEt
3
) and trans -
[PtBr
4
(PEt
3
) shows six lines (each with
l95
Pt satellites), showing the existence of six
complexes viz, [PtBr
4
Cl(PEt)
3
], [PtBr
3
Cl(PEt)
3
], [PtBr
2
Cl
2
(PEt)
3
] two isomers,
[PtBrCl
3
(PEt)3] and [PtCl
4
(PEt)
3
].

Effect of Quadrupole Moments in NMR
Nuclei with quadrupole moments undergo spin-lattice relaxation rapidly. Therefore
the signal of a nucleus, which is attached to a quadrupole nucleus, is extensively broadened.
The nmr signals of a quadrupole nucleus are broadened so extensively that no spectrum is
obtained.
The quadrupole relaxation process is due to the interaction of electric field gradient
with the quadrupole moment. The field gradient is caused by the asymmetry of the electronic
cloud.
(1) In halide ion, the charge distribution is spherical and gives rise to only small field gradient
at the nucleus (longer t). Hence, halide ions give sharp peaks.
Short Notes on Application of NMR Techniques to Inorganic Molecules

Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,
9


(2) Solutions of I
-
(I
127
= 5/2) show a NMR signal. When iodine is added the triiodide, I
3-
, is
formed destroying cubic symmetry of the iodide ion so that quadrupole broadening becomes
effective and the signal disappears. Broadening depends on the amount of iodine added and
hence the rate constant for the reaction I
-
+ I
2
→ I
3-
can be calculated.

Contact Shifts (NMR of Paramagnetic Species)
The unpaired electron present in the paramagnetic compounds broadens the spectrum
by both dipolar and electron spin-nuclear spin coupling mechanisms. The magnetic moment
of an electron is ~10000 times larger than the nuclear magnetic moment. Therefore,
paramagnetic ions produce large magnetic fields which make dipolar-spin lattice relaxation
very rapid.
If the electron relaxation is very slow, then splittings due to s = ±1/2 will be observed.
If the relaxation is fast, the magnetic nucleus senses only the time-averaged magnetic field of
the two spin orientations and a single peak is observed. Intermediate relaxation rates will
broaden the spectrum. The presence of unpaired electrons makes the electron relaxation very
rapid; this causes a very large chemical shift (~3000-5000 cps) of the resonance in the NMR
spectrum. This is referred to as contact nmr shift.
The relationship between contact shift and magnetic field for proton magnetic
resonance is given as:

Where, ¸
e
gyromagnetic ratio for the electron, ¸
N
is that for the magnetic nucleus, S is the
electron spin multiplicity, AH is (H
complex
- H
ligand
) and Av = (v
complex
- v
ligand
), | is Bohr
megneton and g is the ratio of magnetic moment to the total angular momentum of the
electron.
The condition requisite to observing a contact shift in nmr is

t
e
is electronic relaxation time, t
s
is chemical exchange time and A
N
is the contact interaction
constant (electron spin - nuclear spin coupling constant).
Example: In nickel(ll)aminotroponeiminate, one electron is transferred to Ni(II) from the
ligand. As a result, the unpaired electrons present at o and ¸ positions are aligned with
magnetic field while that at | is anti-aligned with the field. o and ¸ carbons have positive
spin density and | carbon negative spin density, i.e., o and ¸ protons are shielded and |
proton is deshielded.
Short Notes on Application of NMR Techniques to Inorganic Molecules

Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,
10




Fluxional Behaviour
These molecules possess more than a single conformation representing an energy
minimum. Several such minima may be present and accessible with ordinary thermal
energies. NMR techniques are very useful in studying fluxional molecules.
The fluxional behaviour is studied by taking NMR spectrum at lower and higher
temperatures. At lower temperature, the rate of fluxional behaviour will be slow and we can
obtain individual lines for each site. At higher temperature, due to inter – conversion, a time –
averaged spectrum will result. For example:
1) A complex formed between tetramethylallene and iron carbonyl
Below -60 °C the H nmr shows three peaks in the ratio 1:1:2 representing the three cis
– proton, three trans-protons and six protons in a plane perpendicular to C – Fe bond. As the
temperature is raised, the spectrum collapses to a single resonance for the average
environment of the 12 protons as the iron migrates around the allene t-system.
C
C H
3
CH
3
C H
3
CH
3
Fe(CO)
4
C
C H
3
CH
3
C H
3
CH
3
Fe(CO)
4

2) q
3
-allyl complex
The HNMR spectrum at low temperature shows two doublets, representing the cis-
and trans- protons and one multiplet, corresponding to the non-terminal hydrogen. Upon
warming, the spectrum changes with collapse of the two doublets into one, establishing that
there are four terminal hydrogen atoms and one non-terminal hydrogen atom. This change is
due to the rapid inter-conversion, which makes H
s
and H
a
indistinguishable.
C
C
C
H
a
H
b
H
a
H
b
H
M
C
C
C
H
a
H
b
H
a
H
b
H
M
C
C
C
H
a
H
b
H
a
H
b
H
M


Short Notes on Application of NMR Techniques to Inorganic Molecules

Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,
11


3) Mercury cydopentadienyl compound, cp
2
Hg
This complex shows two conformers (a) and (b). In (a) the divalent Hg is o bonded to
two q
3
-C
5
H
8
rings. In (b) it is an ionic compound, a q
5
-complex. Structure (a) shows 3
protons resonances with intensity ratio 1:2:2, whereas all the protons are equivalent in (b).
The Hnmr spectrum at -70
o
C shows a single peak.
Hg
H
H
Hg
2+
(a)
(b)

4) Ferrocenophane
A sharp singlet for the methylenic protons and two narrow multiplets for the α and | protons.

5) P
31
nmr spectrum of PF
4
NMe
2
shows triplets of triples (two equatorial and two axial F's
interact separately with P
31
signal) at low temperature and on warming, it gives a regular
quintet (all the four F's become equivalent).
P
F
F
N
F
F
CH
3
CH
3