278 NMR SPECTROSCOPY-APPLICABLE ELEMENTS / Phosphorus-31
Probably the best approach makes use of gated dec-
oupling in order to suppress the NOE effect, long
relaxation times, and an effective relaxation reagent
with a nonspecific effect for all the nitrogens present.
Even traces of paramagnetic impurities in sample,
which act preferentially on certain molecular struc-
tures, can make quantitative analysis impossible.
On the other hand, 15N chemical shifts and nJ(15N,
X) (especially nJ(15N,1H)) can be used successfully
for relative quantication, e.g., tautomeric equilibria,
in cases of fast exchange on the NMR time scale
when average values of the above-mentioned char-
acteristics are observed experimentally.
See also: Nuclear Magnetic Resonance Spectroscopy:
Instrumentation. Nuclear Magnetic Resonance Spec-
troscopy Techniques: Multidimensional Proton; Solid-
State. Peptides.
Further Reading
Buchanan GW (1989) Applications of 15N NMR spectros-
copy to the study of molecular structure, stereochemistry
and binding phenomena. Tetrahedron 45: 581604.
Levy GC and Lichter RL (1979) Nitrogen NMR. New
York: Wiley.
Marek R and Lycka A (2002) 15N NMR spectroscopy in
structural analysis. Current Organic Chemistry 6: 3566.
Phosphorus-31
R M Twyman, University of York, York, UK
& 2005, Elsevier Ltd. All Rights Reserved.
This article is a revision of the previous-edition article by Janice K
Gard, William B Wise, and John C Burquin, pp. 34623470, &
1995, Elsevier Ltd.
Introduction
Phosphorus occurs predominantly as the isotope 31P,
which has a nuclear spin value of 1/2 and is therefore
visible in nuclear magnetic resonance (NMR) spec-
trometry. Phosphorus NMR (31P NMR) has been in
use since the development of multinuclear, high-eld
Fourier-transform instruments in the late 1970s. The
31
P NMR method is widely used, with both one-
dimensional (1D) and multidimensional techniques,
in such diverse areas as the characterization of
organic and inorganic molecular structures, the ana-
lysis of biological uids, the determination of intra-
cellular pH, the noninvasive study of intact tissues
and organs, and quantitative assays of industrial
Martin GE and Hadden CE (2000) Long-range 1H15N
heteronuclear shift correlation at natural abundance.
Journal of Natural Products 63: 543585.
Martin GJ, Martin ML, and Gouesnard JP (1981) 15N-
NMR spectroscopy. NMR Basic Principles and Progress
18: 1.
Mason J (1981) Nitrogen nuclear magnetic resonance
spectroscopy in inorganic, organometallic and bio-
inorganic chemistry. Chemical Reviews 81: 205227.
Mason J (ed.) (1987) Nitrogen. In: Multinuclear NMR,
ch. 12. New York: Plenum Press.
von Philipsborn W and Muller R (1986) 15N-NMR
spectroscopy New methods and applications. Ange-
wandte Chemie (International Edition in English) 25:
383413.
Witanowski M and Web GA (eds.) (1973) Nitrogen NMR.
London: Plenum Press.
Witanowski M, Stefaniak L, and Webb GA (1977) Nitro-
gen NMR spectroscopy. Annual Reports on NMR
Spectroscopy 7: 117291.
Witanowski M, Stefaniak L, and Webb GA (1981) Nitro-
gen NMR spectroscopy. Annual Reports on NMR
Spectroscopy 11B: 1502.
Witanowski M, Stefaniak L, and Webb GA (1986) Nitro-
gen NMR spectroscopy. Annual Reports on NMR
Spectroscopy 18: 3761.
Witanowski M, Stefaniak L, and Webb GA (1993) Nitro-
gen NMR spectroscopy. Annual Reports on NMR
Spectroscopy 25: 14801.
products. In many routine applications, 31P NMR
can now be carried out in a fully automated manner.
Used in conjunction with other NMR-visible nuclei,
the quantitation and full structure elucidation of a
host of disparate species is possible. This article
provides an overview of 31P NMR technology and
some of its major applications.
General Properties and
Chemical Shifts
The chemical shift (d) is a sensitive indicator of the
chemical environment around the phosphorus atom.
It relates closely to the molecular structure, and
under some circumstances even facilitates stereo-
chemical identication. The unique chemistry of
phosphorus-containing materials is partially attrib-
utable to the variable oxidation state of 31P, the parti-
cipation of d orbitals in bonding, and the ability of
the phosphorus atom to vary its coordination
number between 1 and 6.
 NMR SPECTROSCOPY-APPLICABLE ELEMENTS / Phosphorus-31 279

Table 1 Chemical shift ranges of selected phosphorus compounds, referenced to 85% H3PO4 with downeld shifts dened as
positive. Biological compounds are degassed perchloric acid muscle extracts at 37.71C, pH 7.2, K counterion (from Gorenstein)

Compound/class General structure d (ppm) Comments

Inorganic compounds
Orthophosphate 0.0 85% H3PO4
Protonated sodium tripolyphosphate a
11.5
[O3PaOPb(O2)OPaO3]5
5 H b
23.9
Protonated tetrapolyphosphate a
11.5
[O3PaOPb(O2)OPb(O2)OPaO3]6
6 H b
23.9
Phosphorus halides PX3 97.0 XF
220 X Cl
178 CI
H PF6

144
[(CH3)3Si]3CPQAsC[Si(CH3)3]3 688 Coord 2
(CH3)3CP[Cr(CO)5]2 1362
P(NCO)6

388.4 Coord 6
Gaseous P4
552
(CH3)3SiCRP 96 Coord 1
FCRP
207 Coord 1

Organophosphorus compounds
Aliphatic phosphate triesters (RO)3PQO 2.1 R CH3
1.0 R C2H5

0.7 R n -C3H7

3.3 R i -C3H7

1.0 R n -C4H9

13.3 R i -C4H9
Acyclic phosphonates (RO)2RPQO 323.4 R OCH3
30 R OC2H5
27.4 R C3H7
Acyclic phosphites P(OR)3 139.7 R CH3
137.6 R C2H5
137.5 R i -C3H7
138.1 R t -C4H9
[CH2P(C6H5)2=P+P(C6H5)2CH2]
232 Coord 2
R3P
240 RH

62 R CH3

20.1 R C2H5
20.1 R i -C3H7
61.9 R t -C4H9

Biological compounds
Triose phosphates 4.13
Adenosine 5-monophosphate (AMP) 3.44
Orthophosphate 2.20
Glycerol 3-phosphorylcholine
0.13
Phosphocreatine
2.89
Adenosine triphosphate (ATP) a
10.87
b
20.50
g
6.19
Adenosine diphosphate (ADP) a
10.61
b
6.33

Phosphorus compounds give resonances in char-
acteristic ranges depending primarily on the oxi-
dation state and coordination number of the
phosphorus atoms present (Table 1). Chemical shifts
also depend on the pH, concentration, and salt con-
tent of the solution, solvent effects, and the electro-
negativity of any substituents. Since the phosphorus
atom is a comparatively reactive center, it can usually
be found at or near an active site of interest. In gen-
eral, phosphorus chemical shifts are referenced to an
external standard. This requires minor corrections to
be made because of differences in the bulk properties
of the samples. The primary 31P reference is 85%
phosphoric acid placed in a sealed spherical contain-
er or cylindrical capillary tube. A number of second-
ary external and internal standards have been used
280 NMR SPECTROSCOPY-APPLICABLE ELEMENTS / Phosphorus-31
for specialized applications, including 0.2 mol l
1
phosphoric acid in 14% aqueous perchloric acid,
aqueous disodium methylenediphosphonate, deute-
rated phosphoric acid (D3PO4), trimethyl phosphine
oxide, trimethylphosphonate, P4O6, phosphocrea-
tine, and hexachlorocyclotriphosphazene in C6D6.
The chemical shift is sensitive to changes in the
chemical environment, as is spinspin coupling ( J).
Examples of this sensitivity are listed in Table 1,
which also gives examples of the wide variety of co-
ordination numbers and oxidation states of phos-
phorus. 31P chemical shifts cover a wide range.
Dissolved or gaseous diamagnetic phosphorus com-
pounds span B1900 ppm. For dissolved paramagne-
tic phosphorus compounds, this range extends to
B2600 ppm, with OsCl4P[(n-C4H9)2C6H5]2 ob-
served at B1219 ppm. While it is beyond the scope
of this article to provide a comprehensive list of 31P
chemical shifts, further details can be found in the
books and articles listed in the bibliography. The
chemical shift is not the only parameter available for
probing the molecular environment of a phosphorus
atom. Pairs of phosphorus atoms can couple to each
other, and individual phosphorus atoms can couple to
13
C and 1H atoms. 31P13C and 31P1H couplings are
sensitive to the stereochemical relationship between
the coupling nuclei. Used together with carbon chemi-
cal shifts, the conformation and stereochemical fea-
tures of many chemical systems can be deduced.
1
H31P couplings have been studied through one to
four bonds and exhibit a dependence on the molec-
ular conformation and geometry. Examples of the
different types of couplings are shown in Table 2.
The use of homonuclear and heteronuclear coupling
constants and multinuclear (e.g., 31P, 1H, and 13C)
NMR data allows the structure of monophosphorus
31
Table 2 Typical P coupling constants
Compound Phosphorus atom
coupling
constant (Hz,
absolute value)
PH3 186 JPH
P(CH3)3 2.7 JPH
FCRP 182 JPF
K PF6
710 JPF
PF5 B1000 JPF
OP(CH3)3 68 JPC
P(CH2CH3)2 13.7 JPCH
0.5 JPCCH
[O3PaOPb(O2)OPaO3]5
5 H 16.7 JPa Pb
[O3PaOPb(O2)OPb(O2)OPaO3]6
6Na 19.9 JPa Pb
16.7 JPa Pb
Mo(CO)5P(OCH3)3 217 JPMo
(EtO)2P(O)SeP (NEt2)3O(Se)P(OEt)2 17 2JPP
420 1JPse
and polyphosphorus compounds to be determined
fully.
Instrumentation and Sample
Requirements for 31P NMR
Many contemporary NMR spectrometers are capa-
ble of operating in multinuclear mode, and 31P NMR
can be performed in most cases simply by tuning
the NMR probe to the phosphorus frequency and
carrying out the necessary calibrations. Common
31
P resonance frequencies (MHz) and magnetic eld
strengths (T) are 80.96/4.7, 121.44/7.05, 161.92/9.4,
and 202.4/11.75.
The signal-to-noise ratio is dependent on many
variables, not all of which can be controlled by the
operator. These include the volume of sample, the
magnetic eld strength (B0), the magnetic probe
design, spectral accumulation time, relaxation times
T1 and T2, and sample concentration. With the wide
range of available instruments, 31P NMR can be per-
formed on samples ranging in size from a few micro-
liters, through a few tenths of a milliliter to several
milliliters, using respectively a microprobe, a 5 mm
probe, and a 10 mm probe. When the operator is
limited to a given sample and a single type of instru-
ment, the most sensitive probe for 31P measurements
should be chosen, and the sample should be concen-
trated as much as possible, since this helps to decrease
accumulation time and improve sample throughput.
Nevertheless, reasonable spectra can be obtained with
sample concentrations in the range 15 mmol l
1.
Faced with dilute samples, proper presentation of
the sample and accurate spectrometer calibrations
are particularly important. The sample should be
mobile rather than bound, deoxygenated, and free
of particulates. The removal of particulates by ltra-
tion makes a signicant improvement to spectral
quality. High-resolution solution work usually re-
quires dissolution in a deuterated solvent for instru-
mental locking. However, excellent spectra can often
be obtained in protonated solvents in the presence
of a concentrically placed sealed capillary tube
containing the deuterated solvent. This approach is
unsuitable for intact biological samples where the
NMR probe and coil assembly is designed around
the specimen.
As with other nuclei, the highest 31P signal-to-
noise ratio is obtained when the following operations
are performed:
* Optimization of magnetic eld homogeneity
(shimming).
* Calibration of the observe coil 901 pulse width (p/2).
 NMR SPECTROSCOPY-APPLICABLE ELEMENTS / Phosphorus-31 281

* Determination of the inherent relaxation times R1 O S A R1 = R2 = Me

of the sample (T1) and the ensuing pulse repeti- B R1 = Me R2 = Et
P C R1 = Me R2 = iPr
tion rate. D R1 = R2 = Et
* R2 O SH
Choice of sufcient numbers of data points to E R1 = Et R2 = iPr
digitize the data adequately. F R1 = R2 = iPr
* Collection of sufcient time-averaged transients.
C
E
B
Applications of 31P NMR Spectroscopy
One-Dimensional Methods

Useful information can often be obtained by collect- D F

ing a normal 1D survey (semiquantitative) spectrum
A
employing gated proton decoupling and rapid repeti-
tion conditions (i.e., a ip angle o901 and a rela-
tively short recycle time). Species can be identied
by the observation of chemical shifts and relative
concentrations from integration of the resonances. 82 80 ppm
90 88 86 84
In many cases, the 1D spectra are sufciently (A)
complicated to prohibit a straightforward analysis.
For example, Figure 1A shows the reaction products
from the alcoholysis of P4S10 with methanol,
ethanol, and isopropanol. In this case, the selective
use of techniques commonly employed in 13C NMR,
such as the attached proton test (APT), distortionless
enhancement through polarization transfer (DEPT),
and insensitive nucleus enhancement through polari- (B)
zation transfer (INEPT), can yield simplied results.
These methods facilitate the identication of appro- Figure 1 (A) 32.44 MHz 31P spectrum of the alcoholysis pro-
priate functional groups surrounding the 31P atom. ducts of P4S10 with methanol, ethanol, and isopropanol. The
sample is dissolved in toluene, with external C6D6 as the eld
Coding of the heteronuclear coupling into an
frequency lock. (B) The 31P APT spectrum of the same mixture,
observable intensity modulation of the 31P signals showing the encoding of functional group and multiplicity infor-
is achieved using appropriately chosen delays in the mation into the intensity and phase of the resonances. (Reprinted
pulse sequences and decoupler gating. The intensity from Jancke H, Radeglia R, Neels J, and Porzel A (1984)
of the observed 31P signal in these experiments Application of the attached proton test technique in 31P NMR spec-
troscopy. Organic Magnetic Resonance 22: 376378; & Wiley.)
depends on the number of protons, the hetero-
nuclear coupling constant, and pulse delays (often
represented by t) as is shown in the APT spectrum in
such cases, multinuclear multidimensional techni-
Figure 1B. Appropriate analysis of the intensity pro-
ques become more suitable.
les as a function of the delays then results in a
complete identication of the complex mixture. Fur-
Two-Dimensional Methods
ther verication can be achieved by collecting the
1
H-coupled 31P spectrum. Little use has been made Homonuclear NMR Structural elucidation be-
of the INEPT method in 31P NMR experiments comes much more difcult as spectral complexity
because optimization of the correct timing intervals increases. Under these circumstances, proton NMR
is difcult due to the presence of numerous 1H31P spectroscopy has beneted considerably from the use
couplings. However, a greater than 10-fold enhance- of 2D NMR techniques. For example, homonuclear
ment can result from the use of polarization transfer correlation spectroscopy (COSY) identies spin-
procedures. This translates into a factor of 100 or coupled pairs of nuclei as well as spin-coupled net-
more in time savings during data accumulation. works of nuclei in a molecule, even without prior
However, where small (i.e., long-range) coupling structural information. The 2D J-resolved spectro-
constants are involved, longer delays are necessary scopy method permits even highly overlapping reso-
in the pulse sequence. During these delays, the nances to be resolved into readily interpretable
observable signal diminishes due to relaxation pro- multiplets. This enables chemical shift assignments
cesses, resulting in lower signal-to-noise ratios. In to be made in a very straightforward manner. Both of
282 NMR SPECTROSCOPY-APPLICABLE ELEMENTS / Phosphorus-31

these techniques can easily be applied to 31P NMR,
with enormous gains in the detail of spectral infor-
mation.
Figure 2A shows a 31P31P COSY spectrum of a
mixture of phosphate metabolites (ATP, AMP, or-
thophosphate, and pyrophosphate, at two different
pH values). The 1D spectrum shown in Figure 2B is
also present along the diagonal of the contour plot.
The off-diagonal elements, or cross-peaks, connect
pairs of spin-coupled phosphorus resonances to each
other, allowing the entire network to be rapidly
assigned. Such a straightforward analysis is not
possible from the congested 1D spectrum. Along
with connectivity information, the pH of the solution
can be measured noninvasively from the chemical
shift of the inorganic phosphate resonance.
Similarly, homonuclear 31P31P 2D J-resolved
spectroscopy helps simplify even the most crowded
spectra. The 1D spectrum of a dissolved phosphate
glass of average chain length n 4.1 is shown along
the top of Figure 3. Even at 161.9 MHz, the peaks
overlap signicantly. Carrying out a 2D J-resolved
experiment on this sample resolves the indivi-
dual species clearly, with a monotonic increase in

25
c d
b
B C D
20

15

F1 (ppm)
A 10
g
G

0
f
e
E F

0 5 10 15 20 25
(A) F2 (ppm)

0 5 10 15 20 25 ppm
(B)
Figure 2 Two-dimensional homonuclear correlated spectrum (COSY) for a mixture of phosphate metabolites (A) in separate pH
compartments. The 1D experiment (B) is shown below the 31P31P COSY spectrum. The sample consisted of concentric NMR tubes
with the inside pH at 7.5 (designated by capital letters) and the outside at pH 6.5 (lower-case letters). The diagonal peaks labelled Dd,
Ee, Ff and Gg, represent the phosphate resonances of ATP (b-phosphate), AMP, orthophosphate, and pyrophosphate,
respectively. The cross-peak Aa correlates the a- and b-phosphorous resonances of ADP, Bb correlates the g- and b-resonances of
ATP, and Cc correlates the a- and b-resonances of ATP. The resonances were broadened by the addition of GdCl3. (Reprinted from
Van Divender JM and Hutton WC (1982) The application of homonuclear two-dimensional chemical shift correlation maps to the 31P
nuclear magnetic resonances of mixtures of nucleotides involved in cellular bioenergetic process. Journal of Magnetic Resonances 48:
272279.)
 NMR SPECTROSCOPY-APPLICABLE ELEMENTS / Phosphorus-31 283

n=9 7 6 5 4 3 2

15

10

5
F1 (ppm)

10

15

20

4.2 4.6 5.0 5.4 5.8 6.2 6.6

F2 (ppm)

Figure 3 A P P homonuclear 2D J-resolved NMR spectrum of a dissolved sodium phosphate glass with n 4:1 (shown at the
31 31

bottom). The characteristic J-coupling for each species is observed, causing extensive overlap in the corresponding 1D spectrum
shown at the top. The vast simplication obtained by projecting the 2D J-resolved spectrum vertically onto the chemical shift axis
(middle spectrum) clearly delineates the effectively broadband decoupled resonances. All spectra were accumulated at 161.9 MHz
using a 5% (m/m) phosphate solution in H2O with a D2O insert for locking purposes.

chemical shift observed with increasing chain length, projecting the spectrum onto the chemical shift
Pn. The F1 axis displays the coupling constant infor- axis, which is shown above the contour plot. This
mation, while the F2 axis shows the chemical shift of effectively decouples all the resonances from each
each species. Further simplication is achieved by other, yielding individually resolved singlets.
284 NMR SPECTROSCOPY-APPLICABLE ELEMENTS / Phosphorus-31
Heteronuclear NMR As discussed above, complex
spectral information can be simplied greatly by
resolving 31P31P homonuclear interactions into
two dimensions while simultaneously increasing the
information content of the spectra. Using additional
2D modes available on the majority of current
spectrometers, further information can be obtained
by correlating individual phosphorus resonance
alignments with their respective protons. In these
heteronuclear shift-correlated experiments, the
nucleus that is detected can be either 1H or 31P.
Much information can be gained by observing the
phosphorus nucleus in these experiments. One ap-
proach known as 1H-detected heteronuclear multiple
quantum coherence (HMQC) is shown in Figure 4,
applied to the detection of 31P resonances in
d(TGGT)Pt(en), an oligodeoxyribonucleotide adduct
of an anticancer drug. In this example, each 31P reso-
nance was uniquely correlated with the corres-
ponding H30 resonance in the preceding nucleotide
residue; the H50 , H500 resonances were also resolved
4.0
4.5

1H
5.0
5.5
3.0 3.5 4.0 4.5

31P
Figure 4 HMQC contour plot and corresponding 31P (top) and
1
H (side) traces for a 5 mmol l
1 D2O solution of d(TGGT)Pt(en)
at 400 MHz (1H), 201C and pH 7.1. (Reprinted from Byrd RA,
Summers MF, Zon G, Fouts CS, and Marzilli LG (1986) A new
approach for assigning 31
P NMR signals and
correlating adjacent nucleotide deoxyribose moieties via 1H-de-
tected multiple-quantum NMR. Application to the adduct of
d(TGGT) with the anticancer agent (ethylenediamine)dichloro-
platinum. Journal of the American Chemical Society 108:
504505. & 1986, American Chemical Society.)
for the 31P resonances at
2.96 ppm. Subsequent
comparison with 2D nuclear Overhauser effect (NOE)
studies and variable temperature work provided un-
ambiguous assignments of all the 31P resonances.
Heteronuclear shift correlation is not restricted to
1
H and 31P alone. 31P-detected experiments permit
ready observation of rare nuclei, such as 183W and
57
Fe, which are normally difcult to observe. This
approach has been used with success for the
observation of organometallic phosphorus tungs-
ten(IV), rhodium(I), iron(0), iron(II), and nickel(0)
complexes. Indirect observation of insensitive spin
1/2 nuclei offers tremendous gains in sensitivity over
direct observation.
Analytical Aspects
Using many of the techniques often applied to the
study of 1H and 13C, 31P NMR is a powerful tool for
structure elucidation. Observation of the 31P nucleus
opens yet another realm of study quantitation of
the individual species that were previously identied
using the methods described above. Quantitation
requires the optimization of observation conditions
such as pulse width, recycle delay and decoupler
gating, as well as determination of the inherent re-
laxation time of the nucleus, T1. Relative quantita-
tion is then easily achieved, with the area under any
peak directly proportional to the concentration of
the species represented by that resonance. Compa-
rison of the resulting integrals with that of integral
standards yields absolute quantities. The precision of
phosphate assays by 31P NMR is consistently within
0.20.6%, comparable with results obtained using
chromatographic methods.
Indeed, 31P NMR is widely used in a quantitative
fashion. Computer-controlled and automated instru-
ments, used in combination with robotic sample
changers, make the large number of analytical sam-
ples much more manageable. With customized soft-
ware, the spectrometer can automatically accumulate
and store data, perform the Fourier transform and
integration, calculate the relative distribution of spe-
cies present and generate the analytical report. As an
example, Figure 5 shows the output from a routine
oligophosphate assay.
Biological and In Vivo Applications
31
P NMR has also been widely used in biological
investigations. High-resolution NMR has been used
increasingly for the analysis of biological samples
and tissues, allowing the identication and quanti-
tation of all 31P-containing species without further
 NMR SPECTROSCOPY-APPLICABLE ELEMENTS / Phosphorus-31 285

STP Assay Worksheet

Phosphate Mr No. of P Integral Wt% =
(A) (B) (C) (C A)/B (C A)/(BS) 100

STP 367.91 3 58.010 7114.095 91.452

(sodium tripoly)

Trimeta 305.92 3 1.508 153.781 1.977

(sodium trimeta)

TSPP 265.94 2 3.844 511.138 6.571

(tetrasodium pyro)

Ortho 163.94 1 0.000 0.000 0.000

Na3PO4
Sum (S) 7779.013

2 0 2 4 6 8 10 12 14 16 18 20 22 (ppm)
31
Figure 5 121 MHz P spectrum of a 5% (m/m) H2O solution of oligophosphates, with a H3PO4D2O capillary inserted for locking
purposes. The spectrum and analytical report were automatically generated after making only a few menu choices and placing the
sample into the robot sample tray.

purication. NMR has been used to study 31P-con-
taining molecules such as oligonucleotides, nucleo-
tides, proteins, and phosphosugars. Positive
resonance assignments are obtained even in cases of
high spectral complexity, such as the phosphate me-
tabolite mixture shown in Figure 2.
The invention of the surface coil and the
development of NMR probes containing life-support
systems have made it possible to observe high-energy
phosphates in intact tissues and whole organisms. 31P
NMR has been used for the safe, noninvasive detec-
tion of disease states in tissues without risk to the
patient. Metabolic products soluble in the cytoplasm
of skeletal muscle, heart, kidney, brain, and eye have
all been qualitatively observed and identied. With
the appropriate use of standards, determination of
relaxation times, and performance of the necessary
instrument calibrations, quantitative results can be
comparable to those obtained in wet-chemical as-
says. The protonation/deprotonation equilibrium of
phosphates inuences the 31P chemical shift, facilita-
ting the noninvasive determination of tissue pH.
See also: Nuclear Magnetic Resonance Spectro-
scopy: Overview; Principles; Instrumentation. Nuclear
Magnetic Resonance Spectroscopy Applications:
Proton NMR in Biological Objects Subjected to Magic
Angle Spinning.
Further Reading
Chemical Concepts (2001) 31P-NMR Spectral Collection.
New York: Wiley.
Crutcheld MM, Dungan CH, Letcher JH, Mark V, and
Van Wazer JR (1967) 31P Nuclear Magnetic Resonance,
Topics in Phosphorus Chemistry, vol. 5. New York:
Interscience Publishers.
Gard JK, Gard DR, and Callis CF (1992) Quantitative
analysis of inorganic phosphates using 31P NMR spec-
troscopy. In: Walsh EN, Grifth EJ, Parry RW, and Quin
LD (eds.) Phosphorus Chemistry, Developments in
American Science. Washington, DC: American Chemical
Society.
Gard JK, Gard DR, and Callis CF (1992) Quantitative
analysis of inorganic phosphates using P-31 NMR spec-
troscopy. ACS Symposium Series 486: 4155.
286 NMR SPECTROSCOPY-APPLICABLE ELEMENTS / Organometallic Compounds
Gorenstein DG (1984) Phosphorus-31 NMR Principles
and Applications. New York: Academic Press.
Gorenstein DG (1989) P-31 nuclear magnetic resonance of
enzyme complexes bound ligand structure, dynamics,
and environment. Methods in Enzymology 177: 295316.
Gorenstein DG (1992) P-31 NMR of DNA. Methods in
Enzymology 211: 254286.
Lopez-Ortiz F and Carbajo RJ (1998) Applications of po-
larization transfer and indirect detection NMR spectro-
scopic methods based on phosphorus-31 in organic and
Organometallic Compounds
C Pettinari, Universita degli Studi, Camerino, Italy
& 2005, Elsevier Ltd. All Rights Reserved.
Introduction
Nuclear magnetic resonance (NMR) spectroscopy is
one of the most powerful instruments in determining
the structure and properties of an organometallic
compound because of the sensitivity of the chemical
shift to difference in geometry. Also, the term organo-
metallic seems suitable only for compounds having at
least one carbon atom directly linked to a metal, and
the scientific community uses this term also for
compounds in which organic groups are bonded to
nonmetallic elements such as boron, silicon, and
phosphorus. In the rst edition of the Encyclopedia
of Analytical Science, the discussion of the application
of NMR spectroscopy to organometallic chemistry
has been mainly directed to the 1H and 13C NMR
spectra, here the discussion will be addressed mainly
on multinuclear NMR spectroscopy.
NMR spectra of nuclei having a spin quantum
number I 1/2 are generally more easy to investigate
due to a coupling behavior similar to that of 1H.
However, some factors, that could make it difcult to
record and assign an NMR spectrum, need to be
considered: (1) isotopic abundance, (2) sensitivity, (3)
nuclear quadrupole, and (4) relaxation time. For ex-
ample, small molecules having nuclei 1/2 exhibit
generally sharp lines (W1/2 010 Hz), but if the nu-
clei interacts weakly with environments, long relax-
ation times, that make the detection of signals very
difcult, can occur (the T1 for 109Ag is up to 1000 s).
Nuclei having spin with I in the range 19/2 are also
suitable for an NMR investigation; however, these
nuclei possess a quadrupole moment (deviation from
spherical charge distribution) which produces ex-
tremely short relaxation time and extremely large
linewidth W1/2 (up to 50 Hz). If the compounds have
organometallic chemistry. Current Organic Chemistry 2:
97130.
Mitchell T and Costisella B (2004) NMR From Spectra to
Structures: An Experimental Approach. New York:
Springer.
Tebby JC (ed.) (1991) Handbook of Phosphorus-31 Nuclear
Magnetic Resonance Data. New York: CRC Press.
Verkade JG and Quin LD (eds.) (1987) Phosphorus-31
NMR Spectroscopy in Stereochemical Analysis. Deereld
Beach: VCH Publishers.
low molecular weight (small tc) or if the nuclei are
embedded in ligand eld of cubic (tetrahedral, octa-
hedral) symmetry (qzz blocked), narrow lines have
been generally observed (eqn [1]).
2I 3Q2 q2zz tc
W1=2 1
I2 2I
1
where Q is the quadrupole moment; qzz the electric
eld gradient; tc the correlation time; and I the spin
quantum number.
It should also be taken into account that while the
1
H NMR chemical shift is dominated by the dia-
magnetic term, heavier nuclei chemical shifts are
generally dominated by the paramagnetic term. In
Tables 1 and 2 a summary of the NMR properties of
most relevant spins 1/2 nuclei and spins quadrupolar
nuclei, respectively, are reported.
Much of the chemical information in NMR spec-
tra arises from chemical shifts. A decrease in atomic
electron density increases the deshielding, i.e., an
increase in shielding results in a decrease in the
chemical shift, d, i.e., in a shift upeld, i.e., to less
positive/more negative d values. Several factors, such
as coordination number, oxidation state, geometry,
and electronegativity of substituents, inuence the
shielding of the nucleus and hence the chemical shift
in organometallic complexes (Table 3). It is very dif-
cult to nd general rules for the chemical shifts of
nuclei in organometallic compounds since many
interdependent factors are often involved. Shifts
can be very large, up to 20 000 ppm, in metal com-
plexes, often due to strong interaction of metal elec-
trons with the ligands. The geometric factors can
make otherwise equivalent nuclei distinct: in
Fe3(CO)12 (Figure 1) the two bridging carbons will
be distinct from the 10 terminal CO ligands and the
terminal carbonyls on Fe1 will be different from
those on Fe2. So the 13C NMR spectrum will exhibit
different signals for the distinct terminal CO