LECTURE 3

Coupling (Signal Splitting) in 1H-NMR

Spectra
❑ Spin-Spin Splitting (Coupling)
➢Coupling, also referred to as signal splitting or signal multiplicity, is
a third feature of 1H-NMR spectra that provides very useful
information about the structure of a compound.
▪ Coupling is caused by the magnetic effect of nonequivalent hydrogen atoms that
are within 2 or 3 bonds of the hydrogens producing the signal.
▪ Is the Spin-Spin splitting caused by the magnetic field effect of neighbour
nonequivalent hydrogen ( heterotopic hydrogen).
 ❑ Why a proton resonate as doublet when neighboring
another proton?
▪ A proton resonance is effected by the magnetic field of the neighboring proton.
▪ A proton HA ( due to parallel and antiparallel alignment of Hb) will be under
influence of two different magnetic fields and thus resonate at two different
positions as doublet.
➢The distance between individual peaks in the frequency unit is called the
coupling constant and is abbreviated as 3JAB.
• The superscript on the left-hand side shows the number of bonds (double bonds and triple
bonds are counted as single bonds) that separate the coupled protons.
• The subscript on the right-hand side indicates the coupled protons.
• Note that a coupling constant is shared by both groups of coupled protons.
• Because a proton HA has two equal neighboring protons (HB) , thus will
resonate as triplet, and protons HB have only one neighboring proton (HA) so
will resonate as doublet.
Figure : Energy levels for the three different spin states of the methylene protons that
produce triplet and distribution ratio of the magnetic moments in a magnetic field.
• Triplet-doublet coupling and the coupling constant J as shown in the
figure below
➢ Three equivalent HB protons in a magnetic field
will be align in eight different patterns.
When HA proton has three equivalent protons HB on the adjacent carbon atom.
Different alignments of these equivalent protons HB with the applied field may
affect the magnetic field at proton HA in different ways. And therefore a proton HA
will resonate in four different position.
• Quartet-doublet coupling and the coupling constant J as shown in the
figure below
Another example of spin-spin splitting
Another example of spin-spin splitting
General rules for Signal Splitting: Spin–Spin Coupling
1) Chemically equivalent protons do not exhibit spin-spin splitting. The equivalent protons
may be on the same or on different carbon atoms, but their signals do not split.
2) Resonance lines are split by neighboring protons and the multiplicity of the split is
determined by the number of protons. The signal of a proton that has n equivalent
neighboring protons is split into a multiplet of n+1 peaks.
NOTE : The general formula, which covers all nuclei, is 2nl + 1, I being the spin quantum
number of the coupled element.
1) The relative intensities of the peaks and multiplicity can be directly determined from
Pascal's triangle.
2) The distances between the split lines are equal and correspond to the coupling constant
between the coupled nuclei.
triplet n = 2 quartet n = 3 pentet n = 4 sextet n = 5 septet n = 6
 In order to apply Pascal’s triangle the following
rules must be satisfied
(1) If a proton Ha couples to different sets of protons Hb and Hc,
splitting pattern and intensity distribution can be determined by
Pascal's triangle only in cases where the coupling constant Jab is
equal to Jac (Jab= Jac).
(2) So far as the chemical shift difference (∆δ) between the coupled
protons in hertz is much larger than the coupling constant: we can
apply Pascal's triangle to determine splitting pattern and intensity
distribution.

Note: All the 1H-NMR spectra that meet the above criteria are called first-order spectra
(n+1 rule can not be applied)

(n+1 rule is applied)

(3) These rules can be applied only to elements with a spin quantum
number of I = ½ . For example hydrogen (I = ½), but the ones with spin
quantum number greater than ½ such as deuterium D can not be
applied.

Figure 53 Appearance of a triplet arising by the coupling of a proton (a) with two
equal protons and (b) with deuterium.
• The general formula for multiplicity, which covers all nuclei, is given
below, I being the spin number:

K=2nI+1
K=2nI+1 n=2
K= number of lines
I=1
n= number of coupled nuclei
I= Spin number of coupled nucleus
K=5