C13 NMR – How Many

Signals
Chemical Shift Equivalence – How Many Unique Signals? 13C NMR (proton-
decoupled)

Just like with 1H NMR, chemical shift equivalence applies to 13C NMR. A spectrum
produced by a 13C NMR experiment may not always display a 1:1 ratio of signals to
individual carbons atoms. When two or more carbon atoms in a molecule have
chemically equivalent nuclei, instead of producing two or more signals on a 13C NMR
spectrum, they will produce one signal at a specific chemical shift that will represent
those equivalent carbons. In order for atoms to be chemically equivalent, their nuclei
must be interchangeable through the performance of symmetry operations (planes of
symmetry) or rapid intramolecular processes (bond rotation or tautomerization).
Carbon atoms with chemical equivalence may be homotopic (identical) or enantiotopic
(equivalent in achiral solvents).

For the purposes of this topic, we will be dealing with proton-decoupled 13C NMR in
order work with spectra consisting of single line signals rather than multiplets
corresponding to specific carbon atoms.

To start visualize this concept, let’s start with the basic example of methane. Methane
contains one carbon atom. A 13C NMR experiment will produce one signal on a spectrum
at a specific chemical shift, corresponding to the one carbon in methane.

How about ethane? Ethane contains two carbons. Does this mean that two signals will
be produced from a 13C NMR experiment?
While ethane does contain two carbon atoms, two signals will NOT be produced. We can
see by looking at the molecule that ethane contains a mirror plane of symmetry,
bisecting it in half. If we perform a symmetry operation by flipping ethane 180º at a
time (along its C2 mirror plane axis), we can see that the molecule’s carbon atoms are
identical in their environments, making them interchangeable. This results in the
chemical equivalence of the two carbon atoms of ethane, producing a single signal in
a 13C NMR spectrum.

To expand on this, let’s take a look at pentane. How many signals would you expect to
see on its 13C NMR spectrum?
Three signals! Just like in the ethane example, pentane has a mirror plane straight down
the middle. If we flip pentane 180° at a time, we can see three types of carbon atoms
present in the molecule. The pairs of carbons 1 and 5, as well as 2 and 4, are homotopic,
while carbon 3 is distinct. The two homotopic pairs will produce one signal each, while
carbon 3 will produce one for itself. This results in a total of 3 13C NMR signals present
despite pentane containing five carbon atoms.
These rules of symmetry in alkanes apply to alkenes and alkynes the same. Does toluene
have any carbon atoms that are equivalent? How many signals would it produce in a 13C
NMR experiment?

Toluene contains a mirror plane. If we identify that mirrorplane and perform rotational
operations about it, we can see that two pairs of equivalent carbon atoms are present in
addition to three non-equivalent ones. This adds up to a total of 5 different carbon
atoms that will produce signals at 5 separate chemical shifts on a spectrum. Despite the
molecule containing seven carbon atoms total, only 5 signals will be produced.
Let’s try a few examples based on what we’ve gone over so far. How many signals would
each molecule below produce in a 13C NMR experiment?

Each of these compounds produce 3 signals! Like the previous examples, we can
confirm carbon atom equivalence through observing a molecule’s planes of symmetry.

What happens when the symmetry of a molecule is thrown off? If we add a methyl
group to pentane, how many signals would you expect to see on a 13C NMR spectrum of
2-methylpentane?
The addition of this methyl group to pentane will shift the symmetry the molecule.
Instead of observing a bisecting mirror plane, we see a mirror plane that runs straight
through the compound’s aliphatic chain, splitting between its branching carbons.
Symmetry operations can now be performed by flipping the molecule 180° at a time
along this new axis. In doing so, we can see the two carbons of the isopropyl group are
interchangeable and chemically equivalent. Thus, that pair of homotopic branching
carbons will produce one single signal. With the addition of the 4 signals produced by
the remaining non-equivalent carbons in the chain, five signals total will be present on
a 13C NMR spectrum of 2-methylpentane.
As we can see above, molecules with slight structural differences can result in totally
different symmetries that drastically change the number of signals present on a 13C NMR
spectrum.

These two ethers that contain the same number carbon atoms will yield a different
number of signals on a 13C NMR spectrum. Dibutyl ether contains eight carbons but will
produce a total of 4 signals due to its bisecting mirror plane that results in each carbon
atom being part of a homotopic pair. Pentyl propyl ether also contains eight carbons,
but the mirror plane present (running through the chain of atoms) does not bisect the
molecule to make any of the carbon atoms equivalent. This results in pentyl propyl
ether producing a total of 8 signals in a 13C NMR spectrum that represent each of its 8
individual carbon atoms.

How about some regioisomer examples to practice?

While regioisomers contain the same number of carbon atoms, they differ in that their
substituents are positioned in different chemical environments. These structural
differences result in differing symmetries among the molecules, which correspond to
each molecule having different pairs of homotopic carbons. A difference in chemical
environments will cause a difference in chemical shifts, while a difference in quantities
of equivalent and non-equivalent carbons cause a change in the number of signals.

Let’s take a look at a chiral molecule. How many signals would you expect to be
produced from the compound below?
Looking at the molecule, we can see there is a chiral center present at the carbon atom
with a chlorine substituent. The presence of this chiral center eliminates the possibility
of a plane of symmetry that would make any of its carbon atoms equivalent. Therefore,
each of the eight carbons in the compound are distinct, producing 1 signal each on a 13C
NMR spectrum, totaling to 8 signals.

As we can see in the example above, the stereochemistry of a compound can affect the
number of signals produced on a spectrum. What about conformers? Would different
conformations of a molecule always affect the number of signals? Lets take a look at
2,2,3,3-tetramethylbutane.
Just as we observe in 1H MNR, the same chemical equivalence through rapid bond
rotation occurs in 13C NMR. While the rotations of t-butyl groups occur about the central
C-C bond of the compound, they are fast enough relative to the NMR “shutter speed”
that the carbon atoms become equivalent, blurring together like the spinning of a
bicycle wheel or blades of a fan. The resulting signal produced on the spectrum that
corresponds to these atoms will represent the average of the carbon atoms in the
different conformers. So in this case, conformers can be ignored and a total of two
signals will be visible on a spectrum. It is important to remember that unlike 1H NMR, 13C
NMR peak ratios are not to be used quantitatively. This spectrum only supplies the
qualitative information that there are two types of carbon atoms present in the
molecule. It does not specify any quantities of its primary and tertiary carbons.

Let’s apply the information we’ve learned so far to some practice problems.
Just as in 1H NMR, a molecule’s symmetry will greatly affect the number of signals it
produces on a 13C NMR spectrum. Finding any mirror planes present and performing the
necessary symmetry operations greatly simplifies predicting the outcomes of this
spectroscopic method.