ORDER OF A SPECTRUM

The “weak coupling” or “first order” approximation assumes that, for simple coupled systems,
the difference between the Larmor frequencies of the coupled nuclei is large compared to the
coupling (constant) between them:
Δν >> J
The simple multiplicity rules we’ve defined so far for analyzing coupling, for instance, assume
first order: M = 2nI + 1
M = n + 1 (for spin1/2 .)
M is the multiplicity (number of lines in the signal)
n is the number of equivalent coupled nuclei
I is the spin quantum number
The analysis of higher order spectra is more complicated, as multiplicity is no longer governed
by only simple rules

First Order Spectra

If the splitting pattern of a multiplet is given by the n+1 rule, then the spectra is called as ideal or
“first order” spectra. This is usually observed if the spin-coupled nuclei have very different
chemical shifts (i.e. Δν is large compared to J). The chemical shift value and the coupling
constant J can be measured directly from the spectrum.

The first order spectra can be analysed by the following features

1. The multiplicity of a peak is given by the expression 2nI+1, where I is the nuclear spin of the
concerned nucleus and n is the total number of coupled nuclei.
2. The relative intensity of the component peaks of a multiplet is given by the coefficients of the
terms in binomial expansion of (x+1)n for nuclei with I = 1/2.
3. Centre of the multiplet gives the chemical shift of the concerned nucleus.
4. The separations of peaks in two coupled multiplets are exactly equal and correspond to the
coupling constant.

It is well known that the chemical shift measured in Hz depends on the applied magnetic field
and the value of Δν increases as the field strength increases. The value of coupling constant J
remains constant and hence the value of Δν/J will increase on increasing the field strength.
Therefore at high field strength, most 1H NMR spectra become first order. It is important to
notice that high field NMR instruments give better resolution and relatively easily interpretable
spectra.

Second Order Spectra

If the coupled nuclei have approximately same chemical shifts and their chemical shift difference
is comparable to the coupling constant between them, the first order splitting rule (2nI+1) is not
applicable. The splitting pattern in a multiplet is distorted and the bands are no longer
symmetrical. In fact, signal splitting disappears if the chemical shifts of the coupled nuclei are
the same. Such types of spectra are known as second order spectra. It is difficult to measure the
chemical shift and coupling constants values simply by just analysing the spectra.
As the value of Δν/J decreases, the coupled multiplets approach each other and the inner lines
increase in intensity and the outer peaks decrease. In some extreme cases the outer lines may
become too weak to be observed and hence the resulting multiplet is wrongly interpreted. Since
there is leaning of coupled multiplets towards one another and hence the chemical shift values
cannot be given by the centre of the multiplet. In such cases the chemical shift is given by the
centre of gravity. The chemical shift values can be calculated by the following formula:

Nomenclature of spin system

 Pople developed a convenient method to designate the type of spin-coupled systems.

 Each chemically different type of protons is assigned a letter of alphabet A, B, C and so
on.
 Protons which have chemical shifts nearly same are assigned the letters that are close to
one another i.e. A, B and C.
 If the chemical shifts are widely different then the letters which are far apart from one
another are assigned for these protons e.g. A, B, C versus X, Y, Z.
 If groups of nuclei are magnetically equivalent, they are labelled as An, Bn, AnBn etc. For
example CH3 group represents A3 system. The magnetically equivalent protons have
same chemical shift and hence group of one particular magnetically equivalent protons
(An) couple equally with the another group of magnetically equivalent protons (Bn).
 If protons are chemical shift equivalent but not magnetically equivalent, they are labelled
as AA’ system. Thus in systems such as A2B2 or A2X2, the A type protons have identical
coupling with the B type protons. But in AA'XX' system the coupling constants are not
same i.e. JAX ≠ JAX'.
 If three types of protons are involved and they have almost same chemical shifts, the
system is assigned as ABC, whereas protons having widely different chemical shift, a
letter M (letter from the middle of the alphabet) is used to designate the system i.e. AMX.
 In general, a system in which protons has very different chemical shifts display first order
spectra, whereas protons having almost similar chemical shifts display second order
spectra.
The different types of spin systems are described below.
Two-Spin Systems (A2, AB, AX)
1. A2 System
A system having two equivalent nuclei is designated as A2 system. This system always shows a
singlet. The methylene protons in an aliphatic chain with no protons on the adjacent carbon
atoms constitute an A2 system. Compound 1,1,2,2-tetrachloroethane is an good example of A2
system.

2. AB System
A system containing two protons, say HA and HB which couple with each other but do not couple
with any other proton and their chemical shift (δA─δB) values difference is comparable to the
coupling constant JAB. In AB system, both the nuclei are strongly coupled and are designated by
adjacent letters A and B in the alphabet.
In such systems the doublets are distorted i.e. they are not 1:1. The inner lines become larger and
the outer lines smaller.
3. AX System
A system having two protons, say HA and HB with their chemical shift (δA─δB) values difference
much larger to the coupling constant JAB. This system shows two distinct doublets with all the
four lines of equal intensity

Three-spin Systems (A3, AB2, A2B, AX2, A2X, ABC, AMX, ABX)
1. A3 System
A3 system contains three equivalent nuclei and always shows a singlet in NMR spectra.
Examples are CH3I, Cl3CHCH3, CH3COOCH3 (two A3 systems at different chemical shift).

2. AX2, A2X system

In this system, two magnetically equivalent protons are coupled to the third proton which has
chemical shift value widely different from the other two protons.
For such system, NMR spectrum shows a proper doublet (1:1) and a triplet (1:2:1). Examples are
Cl2CHCHClCHCl2.
.
3. AB2, A2B system
In this system, two magnetically equivalent protons are coupled to the third proton which has
comparable chemical shift value to the other two protons. As the ratio of chemical shift values
difference to coupling constant is very small, each line of the doublet is further split into two and
also the centre line of the triplet splits into two and thus producing total eight lines in the
spectrum. In addition, the simultaneous change of spin states of all the three protons produces a
weak signal which is observed only when Δν/J is very small. Thus total 9 lines are possible in an
AB2 or A2B system. The actual appearance of the spectrum depends upon the ratio of chemical
shift to coupling constant (Δν/J). Examples of AB2 or A2B systems are 2,5-dichloronitrobenzene,
2,6-dichloropyridine, pyrogallol etc

4. AMX system
In AMX system, three non-equivalent protons are present with large value of Δν/J. Many vinyl
systems (CH2=CHY) display AMX system (Y is strongly electronegative substituent).
There are three coupling constants for such systems. The trans coupling JMX is larger than the cis
coupling JAX.
JAM is the geminal coupling with a significant value.
The AMX system exhibits 12 lines of almost equal intensity. The coupling constants can easily
be obtained from the analysis of the spectrum. The peaks due to the protons HA and HM are split
into doublet by coupling with HX proton. Each line is further split into narrow doublets. The
doublet of HA will split by HM and similarly the doublet of HM will split by HA.
Similarly the hydrogen HX is split into a doublet by coupling with proton HM and then each line
is further split into doublets with proton HA.

5. ABX system
In ABX system, the chemical shift difference and the coupling constant between two of the three
interacting nuclei are of comparable magnitude and both are coupled to the third nucleus which
has chemical shift very different from both the nuclei. Examples are p-chlorostyrene and
styrene
6. ABX system
In ABX system, the chemical shift difference and the coupling constant between two of the three
interacting nuclei are of comparable magnitude and both are coupled to the third nucleus which
has chemical shift very different from both the nuclei. Examples are p-chlorostyrene and
styrene
In styrene, all the three vinylic protons are non-equivalent and hence have different chemical
shift giving rise to three separate signals. The coupling constant between any two of the protons
(JAB ≈ 2Hz, JAX ≈ 11Hz, JBX ≈ 18Hz) are different. The chemical shift for protons HA and HB are
nearly same but the hydrogen HX has very different chemical shift (downfield) from HA and HB
due to the anisotropy effect of benzene ring. Each of the three signals is split into four lines, a
doublet of doublets. The peak for HX is split into doublet by HB and again each line is split into
doublet by HA. A total of 12 peaks must be observed. Now since the value of JAB is very small
which leads to the overlapping of closely spaced signals observed for HA and HB resulting into
total 4 lines instead of 8 lines due to HA and HB.

7. ABC system

In an ABC system, the chemical shift differences among the three non-equivalent protons are
not large in comparison to the corresponding coupling constant.

The spectrum of such system is complex and exhibits total 15 lines.

The values of coupling constant for such systems can only be calculated using computer
simulation methods.
Manual analysis will lead to approximate values of coupling constants, which in severe cases can
be drastically wrong.

The vinyl system can give ABC system if the electronegativity of the substituent is not much
higher. Example of of ABC system can be allyl bromide

In the ABC system, the chemical shifts of all the three protons are not much different. The
coupling among the protons HA, HB, HC and also CH2 (allylic coupling very less in magnitude)
gives a very complex spectrum. Three multiplets due to HA, HB and HC merge into each other.
The methylene protons can appear as doublet due to coupling with HX, however, sometimes
further splitting in this doublet may be observed due to small allylic coupling with protons H A
and HB.