OpenStax-CNX module: m46151

P-31 NMR Spectroscopy

Nadia Lara
Andrew R. Barron

This work is produced by OpenStax-CNX and licensed under the

Creative Commons Attribution License 3.0

1 Introduction
Phosphorus-31 nuclear magnetic resonance (
31

31

P NMR) is conceptually the same as proton ( H) NMR. The

-1

P nucleus is useful in NMR spectroscopy due to its relatively high gyromagnetic ratio (17.235 MHzT

comparison, the gyromagnetic ratios of

Furthermore,
spin of

31

H and

13

-1

C are (42.576 MHz T

P has a 100% natural isotopic abundance. Like the

/2 which makes spectra relatively easy to interpret.

31

) and (10.705 MHz T

H nucleus, the

31

-1

). For

), respectively.

P nucleus has a nuclear

P NMR is an excellent technique for studying

phosphorus containing compounds, such as organic compounds and metal coordination complexes.

2 Dierences between 1 H and 31 P NMR

There are certain signicant dierences between

H and

to tetramethylsilane [Si(CH3 )4 ], the chemical shifts in

31

31

P NMR. While

H NMR spectra is referenced

P NMR are typically reported relative to 85%

phosphoric acid ( = 0 ppm), which is used as an external standard due to its reactivity. However, trimethyl
phosphite, P(OCH3 )3 , is also used since unlike phosphoric acid its shift ( = 140 ppm) is not dependent
on concentration or pH. As in
standard.

H NMR, positive chemical shifts correspond to a downeld shift from the

However, prior to the mid-1970s, the convention was the opposite.

and papers report shifts using the opposite sign.

Chemical shifts in

31

As a result, older texts

P NMR commonly depend on the

concentration of the sample, the solvent used, and the presence of other compounds. This is because the
external standard does not take into account the bulk properties of the sample. As a result, reported chemical
shifts for the same compound could vary by 1 ppm or more, especially for phosphate groups (P=O).
NMR spectra are often recorded with all proton signals decoupled, i.e.,
This gives rise to single, sharp signals per unique

31

31

P-{ H}, as is done with

13

31

C NMR.

P nucleus. Herein, we will consider both coupled and

decoupled spectra.

3 Interpreting spectra
As in

H NMR, phosphorus signals occur at dierent frequencies depending on the electron environment of

each phosphorus nucleus (Figure 1). In this section we will study a few examples of phosphorus compounds
with varying chemical shifts and coupling to other nuclei.
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1.2: Apr 25, 2013 2:27 pm -0500

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Figure 1: Chemical shift ranges for dierent types of phosphorus compounds.

3.1 Dierent phosphorus environments and their coupling to 1 H

Consider the structure of 2,6,7-trioxa-1,4-diphosphabicyclo[2.2.2]octane [P (OCH2 )3 P ] shown in Figure 2.
The subscripts

and

are simply used to dierentiate the two phosphorus nuclei. According to Table 1, we

expect the shift of P to be downeld of the phosphoric acid standard, roughly around 125 ppm to 140 ppm
and the shift of P to be upeld of the standard, between -5 ppm and -70 ppm. In the decoupled spectrum
shown in Figure 2, we can assign the phosphorus shift at 90.0 ppm to P and the shift at -67.0 ppm to P .

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Figure 2: Structure and decoupled 31 P spectrum (31 P-{1 H}) of P (OCH2 )3 P .

Figure 3 shows the coupling of the phosphorus signals to the protons in the compound.

We expect

a stronger coupling for P because there are only two bonds separating P from H, whereas three bonds
separate P from H (J PCH

>

J POCH ). Indeed, J PCH = 8.9 Hz and J POCH = 2.6 Hz, corroborating our peak

assignments above.

Figure 3: The 31 P spin coupled spectrum of P (OCH2 )3 P .

Finally, Figure 4 shows the

H spectrum of P (OCH2 )3 P (Figure 5), which shows a doublet of doublets

for the proton signal due to coupling to the two phosphorus nuclei.

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Figure 4: 1 H spectrum of P (OCH2 )3 P and proton splitting pattern due to phosphorus.

As suggested by the data in Figure 1 we can predict and observe changes in phosphorus chemical shift
by changing the coordination of P. Thus for the series of compounds with the structure shown in Figure 5
the dierent chemical shifts corresponding to dierent phosphorus compounds are shown in Table 1.

Figure 5: Structure of [XP (OCH2 )3 P Y].

Table 1:

31

P chemical shift (ppm)

P chemical shift (ppm)

90.0

-67.0

-18.1

6.4

51.8

-70.6

P chemical shifts for variable coordination of [XP (OCH2 )3 P Y] (Figure 5). Data from K. J.
Coskran and J. G. Verkade, Inorg. Chem., 1965,

4, 1655.

3.2 Coupling to uorine

19

F NMR is very similar to

19

31

F NMR is a great technique for uorine-containing compounds and allows observance of P-F coupling.

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P NMR in that

19

F has spin

/2 and is a 100% abundant isotope. As a result,

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The coupled

31

P and

19

F NMR spectra of ethoxybis(triuoromethyl)phosphine, P(CF3 )2 (OCH2 CH3 ), are

shown in Figure 6. It is worth noting the splitting due to J PCF = 86.6 Hz.

Figure 6: Structure, 31 P-{1 H} spectrum (A), and

Data from K. J. Packer, J. Chem. Soc., 1963, 960.

19

F-{1 H} spectrum (B) for P(CF3 )2 (OCH2 CH3 ).

3.3 31 P-1 H coupling

Consider the structure of dimethyl phosphonate, OPH(OCH3 )2 , shown in Figure 7.

As the phosphorus

nucleus is coupled to a hydrogen nucleus bound directly to it, that is, a coupling separated by a single bond,
we expect J PH to be very high. Indeed, the separation is so large (715 Hz) that one could easily mistake the
split peak for two peaks corresponding to two dierent phosphorus nuclei.

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Figure 7: Structure and 31 P NMR spectrum of OPH(OCH3 )2 with only the OCH3 protons decoupled.

This strong coupling could also lead us astray when we consider the
phosphonate (Figure 8).

H NMR spectrum of dimethyl

Here we observe two very small peaks corresponding to the phosphine proton.

The peaks are separated by such a large distance and are so small relative to the methoxy doublet (ratio
of 1:1:12), that it would be easy to confuse them for an impurity. To assign the small doublet, we could
decouple the phosphorus signal at 11 ppm, which will cause this peak to collapse into a singlet.

Figure 8: 1 H spectrum of OPH(OCH3 )2 . Data from K. Moedritzer,

19.

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J. Inorg. Nucl. Chem.

, 1961, 22,

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4 Obtaining 31 P spectra
4.1 Sample preparation
Unlike

13

C NMR, which requires high sample concentrations due to the low isotopic abundance of

sample preparation is very similar to

H sample preparation. As in other NMR experiments, a

sample must be free of particulate matter.

0.6-1.0 mL of solvent.

solid will not be analyzed in the NMR experiment. Unlike

31

P NMR

Note that the

H NMR, however, the sample does

dissolved in a deuterated solvent since common solvents do not have

1

C,

A reasonable concentration is 2-10 mg of sample dissolved in

If needed, the solution can be ltered through a small glass ber.

This is true, of course, only if a

13

31

31

not to be

P nuclei to contribute to spectra.

H NMR spectrum is not to be obtained from this sample. Being able to

use non-deuterated solvents oers many advantages to

31

P NMR, such as the simplicity of assaying purity

and monitoring reactions, which will be discussed later.

4.2 Instrument operation

Instrument operation will vary according to instrumentation and software available. However, there are a
few important aspects to instrument operation relevant to

31

P NMR. The instrument probe, which excites

nuclear spins and detects chemical shifts, must be set up appropriately for a

31

P NMR experiment.

For

an instrument with a multinuclear probe, it is a simple matter to access the NMR software and make the
switch to a

31

P experiment. This will select the appropriate frequency for

31

P. For an instrument which has

separate probes for dierent nuclei, it is imperative that one be trained by an expert user in changing the
probes on the spectrometer.
Before running the NMR experiment, consider whether the
protons. Note that

31

31

P spectrum should include coupling to

P spectra are typically reported with all protons decoupled, i.e.,

usually the default setting for a

31

31

1P-{ H}. This is

P NMR experiment. To change the coupling setting, follow the instructions

specic to your NMR instrument software.

As mentioned previously, chemical shifts in

31

P NMR are reported relative to 85% phosphoric acid. This

must be an external standard due to the high reactivity of phosphoric acid. One method for standardizing
an experiment uses a coaxial tube inserted into the sample NMR tube (Figure 9). The 85% H3 PO4 signal
will appear as part of the sample NMR spectrum and can thus be set to 0 ppm.

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Figure 9: Diagram of NMR tube with inserted coaxial reference insert. Image Courtesy of WilmadLabGlass; All Rights Reserved.

Another way to reference an NMR spectrum is to use a 85% H3 PO4 standard sample.

These can be

prepared in the laboratory or purchased commercially. To allow for long term use, these samples are typically
vacuum sealed, as opposed to capped the way NMR samples typically are. The procedure for using a separate
reference is as follows.
1. Insert NMR sample tube into spectrometer.
2. Tune the

31

P probe and shim the magnetic eld according to your individual instrument procedure.

3. Remove NMR sample tube and insert H3 PO4 reference tube into spectrometer.
4. Begin NMR experiment. As scans proceed, perform a fourier transform and set the phosphorus signal
to 0 ppm. Continue to reference spectrum until the shift stops changing.
5. Stop experiment.
6. Remove H3 PO4 reference tube and insert NMR sample into spectrometer.
7. Run NMR experiment without changing the referencing of the spectrum.

5 31 P NMR applications
5.1 Assaying sample purity
31

P NMR spectroscopy gives rise to single sharp peaks that facilitate dierentiating phosphorus-containing

species, such as starting materials from products. For this reason,

for assaying sample purity.

Beware, however, that a clean

31

31

P NMR is a quick and simple technique

P spectrum does not necessarily suggest a

pure compound, only a mixture free of phosphorus-containing contaminants.

31

P NMR can also be used to determine the optical purity of a chiral sample. Adding an enantiomer to

the chiral mixture to form two dierent diastereomers will give rise to two unique chemical shifts in the
spectrum. The ratio of these peaks can then be compared to determine optical purity.

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5.2 Monitoring reactions

As suggested in the previous section,
compounds.

31

P NMR can be used to monitor a reaction involving phosphorus

Consider the reaction between a slight excess of organic diphosphine ligand and a nickel(0)

bis-cyclooctadiene, (1).

(1)
The reaction can be followed by

31

P NMR by simply taking a small aliquot from the reaction mixture and

adding it to an NMR tube, ltering as needed. The sample is then used to acquire a

31

P NMR spectrum

and the procedure can be repeated at dierent reaction times. The data acquired for these experiments is
found in Figure 10. The changing in

31

P peak intensity can be used to monitor the reaction, which begins

with a single signal at -4.40 ppm, corresponding to the free diphosphine ligand. After an hour, a new signal
appears at 41.05 ppm, corresponding the the diphosphine nickel complex. The downeld peak grows as the
reaction proceeds relative to the upeld peak. No change is observed between four and ve hours, suggesting
the conclusion of the reaction.

Figure 10: 31 P-{1 H} NMR spectra of the reaction of diphosphine ligand with nickel(0)
cyclooctadiene to make a diphosphine nickel complex over time.

There are a number of advantages for using

1

31

bis

P for reaction monitoring when available as compared to

H NMR:

There is no need for a deuterated solvent, which simplies sample preparation and saves time and
resources.

The

31

P spectrum is simple and can be analyzed quickly. The corresponding

H NMR spectra for the

above reaction would include a number of overlapping peaks for the two phosphorus species as well as
peaks for both free and bound cyclooctadiene ligand.

31

Purication of product is also easy assayed.

P NMR does not eliminate the need for

not appear in a

31

H NMR chacterization, as impurities lacking phosphorus will

P experiment. However, at the completion of the reaction, both the crude and puried

products can be easily analyzed by both

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H and

31

P NMR spectroscopy.

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10

5.3 Measuring epoxide content of carbon nanomaterials.

One can measure the amount of epoxide on nanomaterials such as carbon nanotubes and fullerenes by
monitoring a reaction involving phosphorus compounds in a similar manner to that described above. This
technique uses the catalytic reaction of methyltrioxorhenium ((2)).
orhenium to form a ve membered ring.

An epoxide reacts with methyltriox-

In the presence of triphenylphosphine (PPH3 ), the catalyst is

regenerated, forming an alkene and triphenylphosphine oxide (OPPh3 ). The same reaction can be applied
to carbon nanostructures and used to quantify the amount of epoxide on the nanomaterial. (3) illustrates
the quantication of epoxide on a carbon nanotube.

(2)

(3)
Because the amount of initial PPh3 used in the reaction is known, the relative amounts of PPh3 and OPPh3
can be used to stoichiometrically determine the amount of epoxide on the nanotube.

31

P NMR spectroscopy

is used to determine the relative amounts of PPh3 and OPPh3 (Figure 11).

Figure 11: 31 P spectrum of experiment before addition of Re complex (top) and at the completion of
experiment (bottom).

The integration of the two

31

P signals is used to quantify the amount of epoxide on the nanotube according

to (4).
(4)
Thus, from a known quantity of PPh3 , one can nd the amount of OPPh3 formed and relate it stoichiometrically to the amount of epoxide on the nanotube. Not only does this experiment allow for such quantication,
it is also unaected by the presence of the many dierent species present in the experiment.

This is be-

cause the compounds of interest, PPh3 and OPPh3 , are the only ones that are characterized by
spectroscopy.

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31

P NMR

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11

6 Conclusion
31

P NMR spectroscopy is a simple technique that can be used alongside

H NMR to characterize phosphorus-

containing compounds. When used on its own, the biggest dierence from
to utilize deuterated solvents.

H NMR is that there is no need

This advantage leads to many dierent applications of

31

P NMR, such as

assaying purity and monitoring reactions.

7 Bibliography

K. J. Coskran and J. G. Verkade, Inorg. Chem., 1965,

4, 1655.

M. M. Crutcheld, C. H. Dungan, J. H. Letcher, V. Mark, and J. R. Van Wazer, P31: Nuclear Magnetic
Resonance. Interscience, NY (1967).

130, 5414.

D. Ogrin, J. Chattopadhyay, A. K. Sadana, E. Billups, and A. R. Barron, J. Am. Chem. Soc., 2006,

J. G. Verkade, and L. D. Quin. Phosphorus-31 NMR Spectroscopy in Stereochemical Analysis. VCH,

W. Guo, K. F. Kelly, A. R. Barron and W. E. Billups, J. Am. Chem. Soc., 2008,

K. Moedritzer, J. Inorg. Nucl. Chem., 1961,

22, 19.

128, 11322.

K. J. Packer, J. Chem. Soc., 1963, 960.

Deereld Beach, FL (1987).

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