Chemical Shifts and Coupling Constants for Hydrogen-1. Part 4

442 Pages·2001·6.587 MB·English

by  R. R. Gupta, M. D. Lechner (eds.)

Landolt-Börnstein
Numerical Data and Functional Relationships in Science and Technology
New Series / Editor in Chief: W. Martienssen
Group III: Condensed Matter
Volume 35
Nuclear Magnetic Resonance
(NMR) Data
Subvolume C
Chemical Shifts and Coupling Constants for Hydrogen-1
Part 4
Inorganic and Organometallic Compounds
Editors
R.R. Gupta, M.D. Lechner
Authors
R.R. Gupta, N. Platzer
1 3
ISSN 1615-1925 (Condensed Matter)
ISBN 3-540-41059-7 Springer-Verlag Berlin Heidelberg New York
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Zahlenwerte und Funktionen aus Naturwissenschaften und Technik, Neue Serie
Editor in Chief: W. Martienssen
Vol. III/35C4: Editors: R.R. Gupta, M.D. Lechner
At head of title: Landolt-Börnstein. Added t.p.: Numerical data and functional relationships in science and technology.
Tables chiefly in English.
Intended to supersede the Physikalisch-chemische Tabellen by H. Landolt and R. Börnstein of which the 6th ed. began
publication in 1950 under title: Zahlenwerte und Funktionen aus Physik, Chemie, Astronomie, Geophysik und Technik.
Vols. published after v. 1 of group I have imprint: Berlin, New York, Springer-Verlag
Includes bibliographies.
1. Physics--Tables. 2. Chemistry--Tables. 3. Engineering--Tables.
I. Börnstein, R. (Richard), 1852-1913. II. Landolt, H. (Hans), 1831-1910.
III. Physikalisch-chemische Tabellen. IV. Title: Numerical data and functional relationships in science and technology.
QC61.23 502'.12 62-53136
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Editors
Gupta, R.R.
Department of Chemistry,
Rajasthan University,
Jaipur- 302004, India
Lechner, M.D.
Institut für Physikalische Chemie,
Universität Osnabrück,
D-49069 Osnabrück, Germany
Authors
Gupta, R.R.
Department of Chemistry,
Rajasthan University,
Jaipur-302004, India
Introduction
Platzer, N.
ICSN Laboratoire de RMN Biologique,
Avenue de La Terrasse,
91198 Gif sur Tvette Cedex, France
Hydrogen-1 NMR data
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Preface
Nuclear Magnetic Resonance (NMR) is based on the fact that certain nuclei exhibit a magnetic moment,
orient by a magnetic field, and absorb characteristic frequencies in the radiofrequency part of the
spectrum. The spectral lines of the nuclei are highly influenced by the chemical environment i. e. the
structure and interaction of the molecules. Magnetic properties of nuclei have been known since 1924 and
the first Nuclear Magnetic Resonance experiment has been made in 1945.
NMR is now the leading technique and a powerful tool for the investigation of the structure and
interaction of molecules. The present Landolt-Börnstein volume III/35 "Nuclear Magnetic Resonance
(NMR) Data" is therefore of major interest to all scientists and engineers who intend to use NMR to study
the structure and the binding of molecules.
In contrast to the 6th Edition of Landolt-Börnstein it is nowadays impossible to include the complete
data in the printed version. The aim of the New Series Edition of Landolt-Börnstein is therefore to store
all data and references in electronic files and selected data and references in the printed version. The
editors have decided to include the complete chemical shifts in the printed version with respect to this
volume. The electronic version on the CD-ROM contains both the complete chemical shifts and the
coupling constants.
Volume III/35 "NMR-Data" is divided into several subvolumes and parts. Subvolume III/35A contains
the nuclei 11B and 31P, and subvolume III/35B contains the nuclei 19F and 15N. Subvolume III/35C contains
the nucleus 1H. Subvolume III/35E containing the nucleus 17O is in preparation. The nucleus 13C and other
nuclei will be presented later. Subvolume III/35C is divided into four parts. The present III/35C Part 4
includes inorganic and organometallic compounds. The first part provides aliphatic and aromatic
hydrocarbons, steroids, and carbohydrates, the second part will present heterocycles, and the third part
natural compounds.
The chemical shifts δ (in ppm) are given along with the complete references. The data are arranged
according to the compounds. The arrangement of the compounds is based on their gross formulae
according to the widely used Hill system. Additionally the complete structural formulae are given for all
compounds.
The complete data, the chemical shifts δ (in ppm) and the coupling constants J (in Hz), including the
structural formulae are available on the provided CD-ROM as PDF-files together with the program Adobe
Acrobat Reader 3.0. You have to install only this program to jump directly into the data files and search
for substances, references, chemical shifts, coupling constants and so on by the fulltext search engine.
Additionally it would be possible to get the computerized data from the electronic version for numerical
calculations and graphical presentations.
The editors kindly acknowledge the support of Dr. R. Poerschke and Dr. H. Seemüller from Springer-
Verlag. The publisher and the editor are confident that this volume will increase the use of the "Landolt-
Börnstein".
Osnabrück, October 2000 The Editors
Survey of Volume III/35
Nuclear Magnetic Resonance (NMR) Data
Chemical Shifts and Coupling Constants
for Boron-11 and Phosphorus-31 Subvolume A
Chemical Shifts and Coupling Constants
for Fluorine-19 and Nitrogen-15 Subvolume B
Chemical Shifts and Coupling Constants
for Hydrogen-1 Subvolume C
Aliphatic and Aromatic Hydrocarbons, Steroids, Carbohydrates Part 1
Heterocycles Part 2
Natural Compounds Part 3
Inorganic and Organometallic Compounds Part 4
Chemical Shifts and Coupling Constants
for Carbon-13 Subvolume D
Chemical Shifts and Coupling Constants
for Oxygen-17 Subvolume E
1 Introduction 1
1 Introduction
The phenomenon of nuclear magnetic resonance (NMR) is based on magnetic properties of nuclei and
therefore they are included here.
1.1 Magnetic properties of nuclei
All nuclei carry a charge and in some nuclei this charge spins on the nuclear axis generating a magnetic
field along the axis. These nuclei behave as tiny bar magnets. The magnetic properties of a nucleus can
be specified in terms of spin number I (I = 0, 1/2, 1, 3/2, 2, 5/2, .....) and the magnetic moment µ of the
nucleus. The magnetic moment of the nucleus is proportional to the spin angular momentum and is
expressed by Eq. (1):
µ ∝ [I(I+1)]½ h/(2π), (1)

µ = γ [I(I+1)]½ h/(2π), (2)

where γ is a proportionality constant known as gyromagnetic or magnetogyric ratio (differing for each
nucleus and essentially measures the strength of nuclear magnets). [I(I+1)]½ h/(2π) is the spin angular

momentum in terms of the spin number I, h is Planck’s constant (6.626.10−34 J/s).
However, the measurable component of the angular momentum is Ih /(2π) and Eq. (2) can be

reduced to Eq. (2a):
γhI
µ ≈ . (2a)
2π
The magnetic moment µ can be also expressed in terms of the Bohr magneton (or nuclear magneton)
by Eq. (3):
µ = g B [I(I+1)]½ h/(2π), (3)
n n
where g is known as the nuclear g-factor (which is determined experimentally). B is the nuclear
n n
magneton defined as eh/(4πm) (e = electronic charge, m = mass of proton) = 5.05.10−24 erg/G.

Each proton and neutron has its own spin and spin number. I is the resultant of these two spins. If the
sum of protons and neutrons (i.e. mass number) is odd, I is half-integer (I =1/2, 3/2, 5/2, ...), if both
protons and neutrons are even-numbered, I is zero (I = 0 denotes no spin) and if the sum is even, I is
integer (I = 1, 2, 3, 4 ...). The magnetic properties of some NMR nuclei are summarized in Table 1.
Nuclei with I > 0 may be called magnetic as they develop the magnetic fields along the axis of spins and
give rise to the phenomenon of nuclear magnetic resonance. Such nuclei do not simply possess magnetic
dipoles, but rather possess electric quadrupoles (it measures the electric charge distribution within a
nucleus when it possesses non−spherical symmetry) and interact with both, magnetic and electric
gradients. The relative importance of the two effects is related to their magnetic moments and electric
quadrupole moments.
Landolt−Börnstein
New Series III/35C,Part-4
2 1 Introduction
1.2 Spinning nuclei in magnetic fields
A spinning nucleus generates a magnetic moment and when placed in an uniform magnetic field H it
tends to align itself with the field. Unless the axis of the nuclear magneton is oriented exactly parallel or
antiparallel to the magnetic field, a certain force is exerted by the applied field. Because the nucleus is
spinning, the effect is that its rotational axis draws out a circle perpendicular to the external field (Fig. 1).
This motion is called precession. The precessional angular velocity of a spinning top is known as Larmor
frequency ω which is proportional to the applied field and can be expressed by Eq. (4) (the gyromagnetic
ratio γ is equal to the ratio of the angular precessional frequency and the applied field):
ω = γ H. (4)
Fig. 1. Spinning nuclei in magnetic fields
Table 1. Magnetic properties of NMR nuclei.
Isotope Natural Spin Magnetogyric Magnetic Electrical
abundance number ratio moment quadrupole
% I γ µ moment
rad/G Bohr magneton e.10−24 cm2
1H 99.9844 1/2 26753 2.79270 −
1
2H 0.156 1 4107 0.85738 2.77.10−3
1
3H − 1/2 − 2.9788 −
1
10B 18.83 3 − 1.8006 0.111
5
11B 81.17 3/2 − 2.6880 3.55.10−2
5
13C 1.108 1/2 6728 0.70216 −
6
14N 99.635 1 − 0.40357 2.10−2
7
15N 0.365 1/2 −2712 −0.28304 −
7
17O 0.037 5/2 −3628 −1.8930 −4.10−3
8
19F 100.00 1/2 25179 2.6273 −
9
29Si 4.70 1/2 −5319 −0.55477 −
14
31P 100.00 1/2 10840 1.1305 −
15
33S 0.74 3/2 2054 0.64274 −5.5.10−2
16
35S − 3/2 − 1.00 4.5.10−2
16
35Cl 75.40 3/2 2627 0.82089 −7.97.10−2
17
Landolt−Börnstein
New Series III/35C,Part-4
1 Introduction 3
Table 1. (cont.)
Isotope Natural Spin Magnetogyric Magnetic Electrical
abundance number ratio moment quadrupole
% I γ µ moment
rad/G Bohr magneton e.10−24 cm2
37Cl 24.60 3/2 2184 0.68329 −6.21.10−2
17
79Br 50.54 3/2 0.34 2.0991 −
35
81Br 49.46 3/2 0.28 2.2626 −
35
127I 100.00 5/2 0.75 2.7937 −
53
183W 14.40 1/2 − 0.177 −
74
The precessional frequency ν can be expressed by Eq. (5):
ω /(2π) = ν or ω = 2πν = γ H, (5)
ν = γ H/(2π). (6)
The Larmor frequency is such that a projection of the angular momentum on the direction of H
always assumes whole multiple of h/(2π) and as such, not all possible precession “cones” occur, only
some selected ones. The number of these possible alignments is 2I+1 for spin I in the direction of
magnetic field. These 2I+1 orientations are quantized in the direction of magnetic field and the
absorbable component m of the spin I can be expressed by Eqs. (7) and (8) for half-integer and integer
spins, respectively:
m = I, I−1, I−2, ..., 1/2, −1/2, ..., −(I−2), −(I−1), −I, (7)
m = I, I−1, I−2, ..., 1, 0, −1, ..., −(I−2), −(I−1), −I. (8)
In each case there are 2I+1 values of m. Each orientation is associated with a different energy level E
and can be expressed by Eq. (9):
γh
E = − µH or E = − H m . (9)
2π
This type of splitting of energy levels in magnetic fields for a nucleus (I > 0) is called nuclear Zeeman
splitting.
1.3 Theory of nuclear resonance
The basis of nuclear magnetic resonance is to induce transitions between the nuclear Zeeman energy
levels. Such transitions are affected by placing an alternating field H perpendicular to the applied field H
a
in such a way that frequency can be altered conveniently. Selection rules permit such transitions between
energy levels 2 and 1 that m − m = ∆m = ± 1 i.e. ∆m = +1 when energy is absorbed (transition is from
2 1
lower to higher energy level) and ∆m = −1 when energy is emitted (transition from higher to lower
energy level). Such transitions from E to E energy levels can be expressed by Eq. (10):
2 1
γh γh γh
∆E = E − E =−( Hm − Hm ) = − H(m − m ). (10)
2 1 2π 2 2π 1 2π 2 1
Landolt−Börnstein
New Series III/35C,Part-4
4 1 Introduction
According to selection rules of quantum mechanics, m − m = ± 1 depending on whether energy is
2 1
absorbed or emitted, Eq. (10) is reduced to Eq. (11):
γhH
∆E = ± . (11)
2π
When the frequency of electromagnetic radiation necessary to induce a transition from one nuclear
spin state to another is exactly equal to the precessional frequency of spinning nucleus, they are in
resonance and the phenomenon of resonance occurs. Thus nuclear resonance (absorption or emission of
energy) occurs when a magnetic nucleus (I > 0) is placed in an uniform magnetic field H and subjected to
electromagnetic radiation of appropriate frequency matching to the precessional frequency of spinning.
Under these conditions the frequency of electromagnetic radiation causing resonance can be expressed by
Eq. (12):
γhH γH
∆E = h ν = , or ν = . (12)
2π 2π
γH
Eq. (12) also exhibits that the precessional frequency ν is .
2π
Eq. (12) correlating electromagnetic frequency causing nuclear resonance with magnetic field
strength is the basis of NMR spectroscopy and from this equation the electro-radiation frequency causing
the resonance for various field strengths can be calculated. Precessional frequencies for some nuclei at
various field strengths are summarized in Table 2.
Table 2. Precessional frequencies as a function of field strength
ν [MHz]
Nucleus H [kG] 14 21 23 47 71 94 117
1H 60.0 90.0 100.0 200.0 300.0 400.0 500.0
1
2H 9.2 13.8 15.3 30.7 46.0 61.4 76.8
1
3H 63.6 95.4 104.5 213.5 322.5 426.9 531.4
1
10B 6.4 9.61 10.5 21.5 32.5 43.0 53.6
5
11B 19.2 28.7 32.0 64.2 96.9 128.8 159.8
5
13C 15.1 22.6 25.1 50.3 75.5 100.8 125.7
6
14N 4.3 6.5 7.2 14.5 21.7 29.1 36.1
7
15N 6.1 9.1 10.1 20.3 30.4 40.7 50.7
7
17O 8.1 12.2 13.6 27.1 40.7 54.5 67.8
8
19F 56.5 84.7 94.1 188.2 288.2 377.6 470.5
9
29Si 11.8 17.8 19.5 39.8 60.1 79.5 99.0
14
31P 24.3 36.4 40.5 81.0 121.5 162.8 202.0
15
33S 4.6 6.9 7.5 15.4 23.2 30.7 38.2
16
35S 7.1 10.7 11.7 23.9 36.1 47.8 59.5
16
35Cl 5.8 8.7 9.6 19.6 29.6 39.2 48.8
17
37Cl 6.9 10.3 11.3 23.0 34.7 46.0 57.3
17
79Br 14.9 22.4 24.5 50.1 75.7 100.3 124.8
35
81Br 16.1 24.2 26.5 54.0 81.6 108.1 134.5
35
127I 11.9 17.9 19.6 40.0 60.5 80.1 99.7
53
183W 2.5 3.67 4.0 8.2 12.4 16.5 20.5
74
Landolt−Börnstein
New Series III/35C,Part-4
1 Introduction 5
1.4 Chemical shift
γH
The fundamental NMR Eq. (12), ν = , exhibits that a single peak should be obtained from the
2π
interaction of radiofrequency energy and the magnetic field on a nucleus as γ is characteristic for a
nucleus. However, the nucleus is shielded by an electron cloud whose density varies with the
environment. This variation gives rise to different absorption positions. Under the influence of the
applied magnetic field electrons circulate and generate their own magnetic field opposing the applied
field and cause a shielding effect. The magnitude of the induced field is proportional to the magnetic
field. The effective magnetic field experienced by the nucleus is changed by this small local field σH
(due to electronic circulation), such that H = H − σH. A nucleus in different environments is
effective
shielded by the circulation of surrounding electrons to different extents. Different values of σH, each
depending on the magnitude of the applied field H are obtained for the nucleus. Because the strength of
the applied magnetic field cannot be determined to the required degree of accuracy, the absolute position
of absorptions cannot be obtained directly from the instrument. However, the relative position of
absorption can readily be obtained with an accuracy of ± 1 Hz. The separation of resonance frequencies
of a nucleus in different structural environments from an arbitrarily chosen standard is termed as
chemical shift. A plot of the chemical shifts (frequencies of absorption peaks) versus the intensities of
absorption peaks, which by integration provides the number of nuclei, constitutes a NMR spectrum. The
chemical shift is symbolized by δ (delta) and is measured in ppm (parts per million) according to Eq.
(13):
ν −ν
δ (in ppm) = 106 . s r , (13)
ν
r
where ν and ν are the resonance frequencies in Hz of the sample s and the reference substance r,
s r
respectively, at constant field H = H = H.
r s
Since field and frequency are linearly related, Eq. (13) can be transformed to Eq. (14):
H −H
δ (in ppm) = 106 . r s , (14)
H
r
where H and H refer to the fields at resonance for the sample s and the reference substance r,
s r
respectively, at constant frequency ν = ν = ν.
r s
The chemical shift in Hz is directly proportional to the applied field H and therefore to the applied
frequency. It is dependent on diamagnetic shielding induced by the applied field. It is the ratio of the
necessary change in field to the reference field or the necessary change in frequency to the reference
frequency and hence a dimensionless number. To spread out chemical shifts i.e. to increase separation of
resonance signals, a high magnetic field is applied which constitutes high resolution NMR spectroscopy.
Chemical shifts are also expressed in an alternative scale, τ, which is related to δ by Eq. (15):
τ = 10.00 − δ . (15)
High values of chemical shifts (δ in ppm) correspond to high frequency shifts (down field or low
field) due to deshielding; and low values correspond to low frequency shifts (upfield or high field) due to
shielding.
Landolt−Börnstein
New Series III/35C,Part-4