Phosphorus-31 NMR

Table 1 Properties of the

Konstantin Karaghiosoff
Universitat Munchen, Munchen, Germany

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Introduction
Nuclear Properties and Standardization
Experimental Techniques
Chemical Shifts
Coupling Constants
Applications of 31 P NMR Spectroscopy
Related Articles
References

INTRODUCTION

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With the discovery of the phenomenon of NMR in bulk

samples in 1945, a new, powerful, analytical method became
available to chemists. The 31 P nucleus was among the first
nuclei to which NMR spectroscopy was applied. Phosphorus31 spectroscopic data have been in the literature since 1951,1,2
and their number increased rapidly in the following years. In
1967 the first comprehensive compilation of 31 P NMR data of
simple phosphorus compounds, as well as a presentation of the
current theory of phosphorus chemical shifts, was published.3
Another publication4 and a review5 cover the literature up to
1969 and to mid-1982, respectively.
With the development of pulse Fourier transform NMR
spectroscopy the sensitivity of the spectrometers improved and
the 31 P NMR experiment became routine. As a consequence
the amount of published 31 P NMR data increased dramatically.
By 1987 it was estimated that more than 40 000 31 P NMR data
items were available in the literature. A Handbook of 31 P
NMR Data contains extensive compilations of representative
data, including coupling constants, for all types of phosphorus
compounds.6 More data can be found in a series of books
dedicated partially7,8 or entirely9 11 to 31 P NMR. A number
of reviews12 14 dealing with the application of 31 P NMR
to transition metal complexes with phosphorus ligands,
and a review15 describing the main developments in 31 P
NMR of transition metalphosphine complexes in the period
19701977, are available.
With modern spectrometers and using all instrumental and
relaxation aids phosphorus compounds at 200 ppm and even
5 ppm concentration levels can be detected by 31 P NMR.9
Due to this capability, 31 P NMR spectroscopy has also gained
importance as an analytical tool in biology and medicine. The
work in this area is documented by a series of reviews16 21
and books.22,23

NUCLEAR PROPERTIES AND STANDARDIZATION

The important properties of the 31 P nucleus for NMR spectroscopy are given in Table 1. Since phosphorus compounds
are generally reactive, no suitable internal reference compound

31 P

Nucleus7,8,10

Natural abundance, C (%)

Nuclear spin, I
Magnetic moment, (N )
Magnetogyric ratio (107 rad T1 s1 )
NMR frequency at 2.35 T (MHz)
Receptivity relative to that of 1 H, D P
Receptivity relative to that of 13 C D C

100
1
2

1.1316
10.8394
40.480
6.63 102
3.77 102

is available for general use. Phosphorus-31 chemical shifts are

referenced to 85% aqueous H3 PO4 as an external standard.
According to the present sign convention shifts are given positive for signals appearing at higher frequency (lower field) with
respect to that of the standard. Great care is recommended,
however, when using data from the older literature, since there
was a change in sign convention in the mid-1970s.
A disadvantage of 85% H3 PO4 as a standard is its broad
resonance signal. A number of secondary external standards,
giving much sharper signals, are therefore in use: P4 O6 ( 31 P
= 112.5), P(OMe)3 ( 31 P = 140.4), PO(OMe)3 ( 31 P = 2.4),
[P(OH)4 ]ClO4 ( 31 P = 0.1), Na2 [CH2 (PO3 H)2 ] in D2 O ( 31 P
= 16.7), (NEt4 )2 HPO4 in H2 O ( 31 P = 2.1).8,9 In some cases
D3 PO4 ( 31 P = 0.3) and (CH3 )3 PO ( 31 P = 72.6) are used as
internal standards.8,9 Alternatively the 2 H internal lock signal
can be used to obtain accurate chemical shifts referenced to
Si(CH3 )4 or to an idealized shift for 85% H3 PO4 . However,
there is little agreement on  for 85% H3 PO4 with values
ranging from 40 480 720 to 40 480 754 Hz.7,9 An absolute
31
P shielding scale is based on gas phase measurements of
PH3 .24
Normally the reported 31 P chemical shifts are not corrected
for diamagnetic susceptibility. In addition temperature, solvent, and concentration dependence of 31 P for both the reference compound and the compounds under study, may be
important. Thus variations in reported chemical shifts for the
same compound of up to 10 units can be encountered in the
literature.7 10
Measurements of the nuclear Overhauser enhancement show
a wide variation extending from zero to the theoretical
maximum of 124%.8,10,25
Spinlattice relaxation times T 1 of phosphorus compounds
vary mostly between 1 and 30 s and can depend strongly
on solvent, temperature, and concentration. Compilations of
T 1 data for simple phosphorus compounds are found in
Mason,8 Verkade and Quin,9 and Berger et al.10 Typical
values are 1.3 s for RPH2 , 39 s for P(OR)3 , 36 s for
PX3 (X = halogen), 29 s for [R4 P]X, 1031 s for R3 P,
630 s for PO(OR)3 , and 211 s for R3 PO.9 For a number
of three-coordinated phosphorus compounds the spin rotation
mechanism has been shown to account for T 1 at ambient
temperature, while at low temperatures dipolar contributions
become important.8 However, P2 t-Bu4 relaxes by a dipolar
mechanism even at ambient temperature. Going to fourcoordination the relative contribution of the spin rotation
mechanism decreases and is still important in the fivecoordinated species PCln Ph5n (n = 24) and the PF6
ion. A rare example, in which chemical shift anisotropy
plays an important role in relaxation, is represented by
Ph3 PO.8

Encyclopedia of Magnetic Resonance, Online 2007 John Wiley & Sons, Ltd.
This article is 2007 John Wiley & Sons, Ltd.
This article was published in the Encyclopedia of Magnetic Resonance in 2007 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470034590.emrstm0393

2 PHOSPHORUS-31 NMR
3

EXPERIMENTAL TECHNIQUES

Due to its favorable nuclear properties (I = 1/2, high

NMR frequency and high receptivity), the 31 P nucleus is
easy to observe and no particular instrumental equipment is
required. Early 31 P NMR spectra of solutions were recorded on
continuous wave instruments and were often poorly resolved.
Now practically all data are obtained with modern FT NMR
spectrometers, equipped either with multinuclear probes or
with separate pretuned probes for 31 P observation, yielding
highly resolved spectra with  1/2 often below 1.0 Hz. The
optimum pulse duration depends on the relaxation time T 1
of the 31 P nucleus and the acquisition time T ac . It has been
recommended to set the pulse duration at cos1 (eTac /T1 ).26
Routine 31 P NMR spectra are obtained with broadband proton
decoupling using a rapid pulse repetition (1 s) and a short pulse
angle (30 ).
A large number of special experimental NMR techniques have been applied to the 31 P nucleus including spin tickling,9 selective27 and broadband9 31 P decoupling, SPT,9 COSY,9 reverse shift heterocorrelated NMR
spectroscopy,9,28 homonuclear9,29 and heteronuclear9,30 J
resolved two-dimensional NMR spectroscopy, EXSY,31 and
Hahn-echo extended pulse sequences.32 The CP MAS technique is widely used to obtain solid state 31 P NMR spectra.9,33
Liquid crystal 31 P NMR spectra of several cyclopolyphosphines (RP)n and of other trivalent and pentavalent phosphorus
compounds have been reported.9 In a few cases reactions of
phosphorus compounds have been studied by CIDNP.34
For 31 P measurements at variable temperature a 0.1 M
solution of triphenylphosphine and triphenylphosphine oxide
in toluene-d 8 has been recommended as a shift thermometer.
At an operating frequency of 40 MHz the change in 31 P is
1.3 Hz per degree.35

d31P
600 500 400

300 200 100

100 200 300 400

Figure 1 Typical ranges of 31 P for differently coordinated phosphorus compounds

CHEMICAL SHIFTS
31

The range of P chemical shifts for liquid, dissolved, or

gaseous diamagnetic phosphorus compounds covers nearly
2000 ppm and extends from +1362 for t-BuP[Cr(CO)5 ]2 to
552 for gaseous P4 . If dissolved paramagnetic compounds
are included, it widens to about 4700, with +3471 for the
complex [(C4 Me4 P)2 U(BH4 )]2 on the high-frequency side and
1219 for OsCl4 (PBu2 Ph)2 on the low-frequency side.9,10
The characteristic ranges of 31 P for one- to six-coordinated
phosphorus compounds are shown in Figure 1. For pentavalent
phosphorus the shift ranges are relatively narrow, and shielding
of the phosphorus nucleus increases as its coordination number
increases from 3 to 6. No such dependence is found for
the trivalent phosphorus and, except for one-coordinated
phosphorus compounds, the shift ranges are much wider.6,36
Detailed bar charts showing the dependence of 31 P for
individual classes of phosphorus compounds on the type of
atoms bonded to phosphorus can be found in Tebby6 and
Mason.8
According to a semiempirical treatment proposed by Van
Wazer and co-workers3,37 phosphorus chemical shifts can
be interpreted in terms of three contributions: the bond
angles at the phosphorus atom, the electronegativity of the
substituents, and the extent of bonding. If only one
parameter is being changed at a time, useful correlations

within a class of compounds are obtained.8,10 Thus for

cyclopolyphosphines (RP)n the phosphorus chemical shift is
almost linearly correlated with the average endocyclic PPP
bond angles, and definite ranges can be established for n =
5 ( 31 P = +50 to 10), n = 4 ( 31 P = 50 to 80), and
n = 3 ( 31 P = 30 to 180). The only known compound
for n = 6, (PhP)6 , ( 31 P = 22) also fits this correlation.8,10
Linear shift/bond angle correlations have also been reported
for the basal phosphorus atoms in cage molecules of the series
P4 Sx Se3x (x = 03), Py As4y S3 , and Py As4y Se3 (y = 04)38
and for differently substituted cyclotriphosphines.39 For 31 P
of tert-phosphines an additive relationship for the alkyl
substituents is found; deshielding of phosphorus increases in
the order Me < Et < i -Pr < t-Bu.7 More additive relationships
have been reported for 31 P in polyphosphines Pn Hn+2 ,40
primary41 and secondary phosphines,42 and alkyl phosphonium
salts.42 Additive relationships often fail, however, when
bonding or electronegative substituents are involved.7,8,10
Theoretical calculations of 31 P chemical shifts for a series
of simple phosphorus compounds by semiempirical methods
and for PH3 by ab initio methods have been reviewed.9 Using
the IGLO method, ab initio calculations of 31 P for larger
molecules have also been performed.43
Isotope effects on 31 P nuclear shielding caused by 2 H, 13 C,
15
N, 18 O, 34,36 S, 35,37 Cl, and 79,81 Br have been observed.44,45

Encyclopedia of Magnetic Resonance, Online 2007 John Wiley & Sons, Ltd.
This article is 2007 John Wiley & Sons, Ltd.
This article was published in the Encyclopedia of Magnetic Resonance in 2007 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470034590.emrstm0393

PHOSPHORUS-31 NMR

In 2-amino-1,3,2-dioxaphosphorinane 2-chalcogenides the isotopic effect of 15 N on 31 P is larger for the shorter equatorial
than for the longer axial PN bond.44
4.1

One-Coordinate Phosphorus

The range of 31 P chemical shifts for one-coordinated

phosphorus compounds (phosphaalkynes RCP6,36,46,47
and [2,4,6-t-Bu3 C6 H2 NP][AlCl4 ]48 ) extends mainly from
+96 to 70. Depending on R, shielding of the phosphorus
nucleus in phosphaalkynes increases generally in the order
(CH3 )3 Si < aryl,H < alkyl < amino < F.36,46 A linear
relationship results for 31 P and N of identically substituted
phosphaalkynes and nitriles.36 Phosphorus-31 solid state
NMR investigations of 2,4,6-t-Bu3 C6 H2 CP49 and [2,4,6t-Bu3 C6 H2 NP][AlCl4 ]50 have been published.
4.2

Two-Coordinate Phosphorus

Compilations of 31 P are available for the large number

of two-coordinated phosphorus compounds.6,51 53 Values of
31 P extend from +954 to 363 with most of them between
+600 and 300. This wide shift range corresponds to a
variation of phosphorus character from a phosphenium type
with a high-frequency chemical shift to a phosphide type with
a low-frequency chemical shift. The overall charge of the
molecule seems not to be important.6,51 Values of 31 P of
fully unsaturated phosphorus heterocycles extend from +495
to 5 with most of the shifts between +300 and +50.6,36,52,53
Linear correlations are found for 31 P in aryl-substituted
phosphaalkenes with Hammett constants and for 31 P in
iminophosphines with the n * transition energies. Values
of 31 P of =PR in various acyclic compounds and 13 C
and 77 Se of the corresponding =CH2 and =Se compounds
also give fair linear correlations. More linear correlations are
found for the exchange of =Pfor =Nin both acyclic and
heterocyclic compounds and for =CHin otherwise identical
heterocycles.36
Solid state 31 P NMR spectra of a diphosphene,54 a
phosphaalkene,49 and benzo-anellated heterophospholes55 have
been reported.
4.3

Three-Coordinate Phosphorus

The 31 P chemical shifts of three-coordinate tervalent

phosphorus cover a wide range from +282 to 461 with most
of the shifts between +220 and 290.6 Ranges of 31 P for
individual types of P (III) compounds are found in Tebby,6
Mason,8 and Berger et al.10 Values of 31 P of conformationally
mobile di- and polyphosphines are likely to be temperaturedependent. In alkenic-substituted phosphines the 31 P nucleus
is more shielded in the Z - compared with the E -isomer (effect
of steric compression). A nearly linear correlation is found
between 31 P in Ph2 PR and 13 C in CH3 R.8 10
For three-coordinate pentavalent phosphorus 31 P ranges
(excluding extreme values) essentially from +300 to +40
and is thus found at higher frequency than 31 P of highercoordinated phosphorus(V).6,36,56 In 3 -phosphoranes of the
type RPXY, depending on the double bonded substituents X
and Y, phosphorus shielding generally increases in the order
MLn < S < Se < CR2 < NR < O.36,56

4.4 Four-Coordinate Phosphorus

The 31 P chemical shift range of pentavalent tetracoordinate

phosphorus extends essentially between +140 and 90 with
a few extreme values for phosphonium compounds of up to
308.6 Shift ranges for individual classes of compounds can
be found in Tebby,6 Mason,8 and Berger et al.10
A number of phosphonic and phosphinic acids, inorganic
phosphates, and polyphosphates have been investigated by
solid state 31 P NMR spectroscopy.10 In the case of polyphosphates, the different 31 P values of the terminal and bridging
phosphate groups have been interpreted in terms of the electronegativity difference between terminal and bridging oxygen atoms (estimated at 0.4) and the difference in -bonding
order.57 A linear relationship results between 31 P and the
PO bond strength in inorganic phosphates.58
In phosphates and phosphate esters, as well as in their thio
derivatives a clear dependence of 31 P on the XPX angle (X
= O,S) is observed. In phosphoric and phosphonic acids, and
in mono- and dinucleotides the 31 P chemical shift shows a
dependence on pH. Good linear Hammett correlations and a
linear 31 P/ 13 C relationship for [Ph3 PR]X and CH3 R have
been reported.10
In contrast to the tetracoordinate phosphorus(V), the 31 P
chemical shift range for the tetracoordinate tervalent phosphorus (phosphoranide-type phosphorus) is much larger and
extends from +222 to 242.6
4.5 Five-Coordinate Phosphorus

The chemical shift of five-coordinate phosphorus covers

a range between +31 and 195 with the majority of shifts
between 0 and 80.6 A temperature dependence of the
NMR spectra is often encountered, due to intermolecular9,59
or intramolecular (pseudorotation)9,60 ligand exchange or to
hindered rotation.9,61
4.6 Six-Coordinate Phosphorus

The chemical shifts of six-coordinate phosphorus are found

between 57 and 441 with most of the shifts between 80
and 290.6 The major factors determining the chemical shifts
are electronegativity and anisotropic effects of the substituents.
Increasing the overall charge of the species from +1 through
zero to 1 shifts 31 P to lower frequency, while incorporation
of the phosphorus in a five-membered ring results in a shift of
31 P in the opposite direction.6,9

5 COUPLING CONSTANTS

Scalar spinspin couplings of phosphorus to almost all

elements of the Periodic Table are known, and remarkably large coupling constants up to 17000 Hz (!) have
been observed. Compilations of phosphoruselement coupling constants can be found in several books.7 10,62 Representative values are contained in most of the compilations of 31 P chemical shift data.4 6,51 53 Specialized reviews
on phosphorusphosphorus,63 phosphorushydrogen,64 and
phosphoruscarbon65,66 coupling constants are available.

Encyclopedia of Magnetic Resonance, Online 2007 John Wiley & Sons, Ltd.
This article is 2007 John Wiley & Sons, Ltd.
This article was published in the Encyclopedia of Magnetic Resonance in 2007 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470034590.emrstm0393

4 PHOSPHORUS-31 NMR
Table 2

Observed PhosphorusPhosphorus Coupling Constants

Coupling constant

J (Hz)

References

55 to 670
157 to 684
67 to +766
35 to +665
28 to +150
11 to 210
0 to 227
2 to 35
5 to 9
3 to 12
1 to 8
1 to 2
4

810,5153,63
810,63
810,63
810,63
810,63
810,63
810,63
9, 10, 63
67
67, 68
67
67
67

J (PIII ,PIII )

1 J (PIII ,PV )
1

J (PV ,PV )
2 J (PIII ,PIII )
2 J (PIII ,PV )
2
J (PV ,PV )
3 J (P,P)
4 J (P,P)
5 J (P,P)
6 J (P,P)
7
J (P,P)
8 J (P,P)
9 J (P,P)

More information on specific phosphoruselement coupling

constants can be found in the references in Tables 2 and 3.
It is generally observed, that the values of the reduced
coupling constants n K (P,X) decrease in the order 1 K (P,X) 
3
K (P,X) > 2 K (P,X) > 4 K (P,X).9 In many cases, however, the
order of 3 K (P,X) and 2 K (P,X) is reversed, due to structural
factors. Coupling constants over more than four bonds are
normally two or more orders of magnitude smaller than
1
K (P,X). In special cases and particularly in compounds with
a delocalized system long-range coupling constants n J (P,P)
for n = 5967,68 and n J (31 P,13 C) up to n = 769 have been
observed.
The presence of a lone pair of electrons at the phosphorus
atom or at the atom coupled with it seems to be associated
with a negative one-bond reduced coupling constant 1 K (P,X).
An exception is provided by 1 K (31 P,1 H), however, which is
positive. The magnitude of 1 K (P,X) increases with increasing
electronegativity of the substituents regardless of its sign. Linear relationships have been found between 1 K (P,X) and the
sum of the electronegativity of the substituents at the phosphorus atom for 1 K (183 W,31 P), 1 K (77 Se,31 P), 1 K (95 Mo,31 P),
1
K (31 P,31 P), 1 K (31 P,13 C), and 1 K (31 P,1 H).9,10,70
In molecules with a trigonal bipyramidal geometry 1 K (P,X)
through the shorter equatorial bond is larger than through
the longer axial bond.9,10,71 In transition metalphosphine
complexes the one-bond phosphorusmetal coupling constant
is found to increase with decreasing trans-effect of the ligand
in the trans-position to the phosphorus atom in the order
MePh2 Si > Ph > Me  R3 P > (PhO)3 P, CN > Et3 As >
NO2 > amine, NCO, NCS > Cl, Br, I > ONO2 > F.9,10 A
bond angle and dihedral angle dependence of 1 K (P,X) has also
been discussed.5,9,72,73
Geminal coupling constants 2 K (P,X) show, in principle, the
same dependences as 1 K (P,X); the signs are often reversed,
however. For the three-coordinate trivalent phosphorus there
is a dependence of 2 K (P,X) on the dihedral angle between
the phosphorus lone pair and the X nucleus,73 which has been
investigated for 2 J (31 P,31 P), 2 J (31 P,13 C), and 2 J (31 P,1 H). For
tetracoordinate phosphorus a similar dependence is found with
an electronegative substituent in place of the lone pair.9
Of general importance is the dependence of vicinal reduced
coupling constants 3 K (P,X) on the dihedral angle between the
phosphorus and the X nucleus (Karplus relationship), which
has been investigated for a number of compounds. In all

cases a minimum near 90 and maxima at 0 and 180 are

observed.9,10,74
5.1 PhosphorusPhosphorus Coupling Constants

Typical ranges for P,P coupling constants are given in

Table 2. The value of 1 J (31 P,31 P) is negative between
trivalent phosphorus atoms and, where the sign is known, also
between trivalent and pentavalent phosphorus atoms. Between
pentavalent phosphorus atoms 1 J (31 P,31 P) is often positive.
One-bond phosphorusphosphorus coupling constants show a
large stereochemical dependence on rotation about the PP
bond, especially when there are lone pairs at the phosphorus
atoms.8 10
Geminal P(III), P(III) coupling constants are mostly positive and extend up to +665 Hz. In acyclic compounds geminal P(III), P(V) couplings range mainly between +50 Hz and
+150 Hz, whereas for cyclic compounds smaller and negative
values are found. The value of 2 J (31 P,31 P) between pentavalent phosphorus atoms in acyclic compounds is generally small
(1143 Hz), but can assume large values up to +210 Hz in
cyclic compounds.8
5.2 Phosphorus Couplings to Other Nuclei

Typical ranges for the coupling constants of phosphorus to other elements of the Periodic Table are given in
Table 3. The signs of the coupling constants, where known,
have also been included. The value of 1 J (31 P,1 H) tends to
increase with increasing oxidation state and coordination number of phosphorus; the individual ranges overlap considerably,
however.70 One-bond phosphorusfluorine coupling constants
show the opposite trend, in accord with the opposite signs
of 1 J (31 P,1 H) and 1 J (31 P,19 F).9,10 An isotope effect of 2 H
on 1 J (31 P,1 H) has been reported.103 The 1 J (31 P,15 N) value is
positive (+24 to +105 Hz) in trivalent, generally positive (44
to +60 Hz) in tetracovalent, and negative (40 to 80 Hz) in
pentacovalent phosphorus compounds. The 1 J (77 Se,31 P) value
is larger for a phosphorusselenium double bond (500 to
1200 Hz) than for a single bond (100 to 500 Hz). Similarly 1 J (125 Te,31 P) is larger for P=Te (13242290 Hz) than
for PTe (80996 Hz).8,9 Exceptionally large values, reaching
orders of magnitude of the corresponding one-bond coupling
constants, are observed for 2 J (77 Se,31 P),92 2 J (119 Sn,31 P),10
2 205
J ( T1,31 P),102 and 2 J (207 Pb,31 P)104 in transition metal complexes.

6 APPLICATIONS OF

31 P

NMR SPECTROSCOPY

Phosphorus-31 NMR spectroscopy has been used to monitor the progress of chemical reactions and exchange equilibria
since its early days. Today 31 P NMR spectroscopy is a powerful diagnostic tool in practically all areas of preparative chemistry where phosphorus is present. Alone, or in combination
with the NMR spectroscopy of other nuclei, it is mostly used
for the identification and structure elucidation of phosphorus
compounds. The enantiomeric purity of chiral alcohols, thiols
(via the corresponding phosphites and thiophosphonates), and
phosphines is conveniently checked by 31 P NMR. Based on

Encyclopedia of Magnetic Resonance, Online 2007 John Wiley & Sons, Ltd.
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This article was published in the Encyclopedia of Magnetic Resonance in 2007 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470034590.emrstm0393

PHOSPHORUS-31 NMR
Table 3

Observed Coupling Constants of Phosphorus to Other Nuclei

Coupling constant

J (Hz)

1 J (31 P,1 H)

110 to 1200
0 to 205
0 to 51
0 to 18
0 to 12
30 to 112
6 to 10
33 to 55
2
2 to 6
9
10 to 217
40 to +500
20 to +90
0 to 26
0 to 7
0 to 26
0 to 2
0 to 2
80 to +105
0 to 55
4 to 9
48 to 220
463 to 1555
2 to 700
0 to 313
6 to 64
4 to 33
90 to 290
11 to 30
7 to 154
1 to 59
3 to 6
105 to 127
100
30 to 40
110 to 510
105 to 153
140 to 405
10 to 149
375 to 1222
161 to 482
1109 to 1458
1275 to 1302
38
100 to 1200
0 to 140
0 to 18
0 to 1
296 to 350
315 to 380
5 to 52
5
1050
90 to 284
254
400 to 909
8 to 374
0 to 34
1 to 24
212 to 1118
220 to 1217
9 to 10

2 J (31 P,1 H)
3

J (31 P,1 H)
4 J (31 P,1 H)
5 J (31 P,1 H)
1 31 2
J ( P, H)
2 J (31 P,2 H)
1 J (31 P,7 Li)
2 J (31 P,7 Li)
2 J (31 P,9 Be)
1 31 10
J ( P, B)
1 J (31 P,11 B)
1 J (31 P,13 C)
2 31 13
J ( P, C)
3 J (31 P,13 C)
4 J (31 P,13 C)
5 J (31 P,13 C)
6 J (31 P,13 C)
7 31 13
J ( P, C)
1 J (31 P,15 N)
2 J (31 P,15 N)
3 31 15
J ( P, N)
1 J (31 P,17 O)
1 J (31 P,19 F)
2 J (31 P,19 F)
3 J (31 P,19 F)
4 J (31 P,19 F)
5 J (31 P,19 F)
1 J (31 P,27 Al)
2 31 27
J ( P, Al)
1 J (31 P,29 Si)
2 J (31 P,29 Si)
3 31 29
J ( P, Si)
1 J (35 Cl,31 P)
1 J (37 Cl,31 P)
2 J (45 Sc,31 P)
1 J (51 V,31 P)
1 53
J ( Cr,31 P)
1 J (55 Mn,31 P)
1 J (57 Fe,31 P)
1 59
J ( Co,31 P)
1 J (61 Ni,31 P)
1 J (63 Cu,31 P)
1 J (65 Cu,31 P)
2 J (71 Ga,31 P)
1 77
J ( Se,31 P)
2 J (77 Se,31 P)
3 J (77 Se,31 P)
4 77
J ( Se,31 P)
1 J (79 Br,31 P)
1 J (81 Br,31 P)
1 J (89 Y,31 P)
2 J (89 Y,31 P)
1 93
J ( Nb,31 P)
1 J (95 Mo,31 P)
1 J (97 Mo,31 P)
1 99
J ( Tc,31 P)
1 J (103 Rh,31 P)
2 J (103 Rh,31 P)
3 J (103 Rh,31 P)
1 J (107 Ag,31 P)
1 109
J ( Ag,31 P)
2 J (109 Ag,31 P)

Sign

References

9, 10, 64
9, 10, 36
9, 10, 36
9, 10, 75
10, 75
76
77, 78
9, 10, 79
80
8
10
8, 9, 81
9, 10, 65
9, 10, 65
9, 10, 65
10, 69
10, 69
69
69
9, 10, 36, 82, 83
30, 82
82
810,84
4, 9, 10
4, 10, 36
4, 10
4, 10
10
810
8, 85
10, 36, 86
10, 36, 87
10
88
88
8
8, 10
8, 89
8
8, 10, 77, 90
810
810,77
810
810
8
810,91
91, 92
91
91
88
88
90
8
9
8, 9
8
10
9, 10, 90
9, 10
9, 10
9, 10
8, 90
8

+
+

+
+

1 J (111 Cd,31 P)
1 J (113 Cd,31 P)
2 J (113 Cd,31 P)
1

J (117 Sn,31 P)

1 J (119 Sn,31 P)
2 J (119 Sn,31 P)
1

J (125 Te,31 P)

2 J (125 Te,31 P)
1 J (183 W,31 P)
2 J (183 W,31 P)
1 J (187 Os,31 P)
1

J (195 Pt,31 P)
2 J (195 Pt,31 P)
3 J (195 Pt,31 P)
4 195
J ( Pt,31 P)
1 J (199 Hg,31 P)
2 J (199 Hg,31 P)
1 J (203,205 Tl,31 P)
2 J (205 Tl,31 P)
1 207
J ( Pb,31 P)
2 J (207 Pb,31 P)

1091 2443
1142 2240
2 80
76 2260
50 3125
83 4269
84 2290
11
80 847
2 24
149 492
62 9150
36 1977
6 245
34
143 17528
40 160
3144,3203
1056 1202
1100 2452
28 3460

+
+
+
+
+
+

9, 93, 94
8, 94
8
7, 10, 95
4, 9, 10, 95, 96
10, 96
810
10
810,90
8, 10
10, 90, 97
810
810,98
9, 10, 99
9
810,100
8, 99
101, 102
8, 10, 102
9, 104
104

the pH dependence of 31 P, the pK a values of phosphoric acids

have been determined. Phosphorus-31 NMR is also extensively
used for the investigation of dynamic processes.9,10
In biochemistry and medicine in vivo 31 P NMR and
31
P NMR imaging gain increasingly in importance.8,105,106
Oxygen-18 isotope effects on 31 P nuclear shielding are extensively used to study the chirality of phosphorus compounds
and the stereospecificity of enzymatic reactions.44

7 RELATED ARTICLES

Brain Neoplasms in Humans Studied by Phosphorus-31

NMR Spectroscopy; Inorganic Chemistry Applications; Membranes: Phosphorus-31 NMR; Nucleic Acids: Phosphorus-31
NMR; Phosphorus-31 Magnetization Transfer Studies In Vivo;
Proton Decoupling During In Vivo Whole Body Phosphorus
MRS; Single Voxel Whole Body Phosphorus MRS; Tissue
Behavior Measurements Using Phosphorus-31 NMR.

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6 PHOSPHORUS-31 NMR
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This article was published in the Encyclopedia of Magnetic Resonance in 2007 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470034590.emrstm0393

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Biographical Sketch
Konstantin Karaghiosoff. b 1956. Ph. D., 1986, University of Munich.
Introduced to NMR by A. Schmidpeter. Inorganic Chemistry, University
of Munich, 1980present. Approx. 50 publications. Research interests
include synthesis and reactions of monocyclic and anellated heterophospholes, phosphorussulfur and phosphorusselenium rings and cages,
31 P and 77 Se NMR spectroscopy, analysis and simulation of high-order
spin systems.

Encyclopedia of Magnetic Resonance, Online 2007 John Wiley & Sons, Ltd.
This article is 2007 John Wiley & Sons, Ltd.
This article was published in the Encyclopedia of Magnetic Resonance in 2007 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470034590.emrstm0393