Figure 4.1 (a) Precession of the angular momentum of a nucleus about the magnetic field axis. The doubleheaded arrow indicates the precession angle. (b) Double precession cone for nuclei with spin I = 1/2, for
which two states with m = +1/2 and m = –1/2 are allowed.
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Figure 4.2 (a) Linear dependence of the splitting of energy levels with the applied magnetic field. (b) Energylevel diagram for the two common cases of nuclei with I = 1/2 and I = 1.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
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Figure 4.3 (a) Schematic drawing of an NMR spectrometer with a superconducting magnet, cooled by liquid
helium and shielded by liquid nitrogen. (b) Details of an NMR probe, showing an inlet for gas to spin the
sample, gas leads for temperature control, and the r.f. coils.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
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Figure 4.4 (a) A pulse experiment consists of a rectangular r.f. pulse of length p followed by a response
signal (an undulating signal called the free induction decay, explained in Section 4.4.3) from the sample,
which is recorded in a receiver. (b) Intensity distribution of excitation by a short high-energy pulse of
frequency 1; in order to have an even distribution of excitation of all frequencies in a spectrum, only a small
part ∆ is used.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
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Figure 4.5 (a) Magnetization of the sample M0 in the z direction and application of a pulse in the x´ direction
results in (b), the tilt of the magnetization by an angle ; this has a component My in the y´ direction. (c) The
result of a 90o pulse in the x´ direction is full magnetization in the y´ direction. (d) The result of a 180o pulse
is inverted magnetization directed along z.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
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Figure 4.6 (a) Magnetization M0 of a sample in its equilibrium state due to a slightly higher population of a
than  spins. (b) Partial phase coherence of some spins and resulting magnetization My in the y´ direction;
note that the spins are shown in the x, y, z frame but that the magnetization refers to the rotating frame x´,
y´, z´. (c) Inverted populations after a 180o pulse.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
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Figure 4.7 Relaxation of the transverse magnetization My´ after a 90° pulse illustrated in two time steps.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
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Figure 4.8 Schematic illustration of the dependence of the relaxation times T1 and T2 on the molecular
tumbling rates, expressed in terms of reciprocal correlation time T -–1c .
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Figure 4.9 (a) FID containing only one damped sine function. Fourier transformation (FT) results in a single
signal offset by the frequency of the FID. (b) FID containing two superimposed damped sine functions.
Fourier transformation results in two signals, each offset by its respective frequency in the FID.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
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Figure 4.10 (a) Absorption signal (real part) and (b) dispersion signal (imaginary part) as the result of a
complex Fourier transformation of an FID. (c) A partially out-of-phase signal, a mixture of unequal parts of
absorption and dispersion contributions.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
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Figure 4.11 11B NMR spectrum of B10H14. All couplings to hydrogen were removed. The boron cage structure
is as shown, so four equivalent (B5, B7, B8 and B10) nuclei give rise to the largest peak, and three pairs of
equivalent nuclei give the three smaller peaks. The assignment is discussed in Section 4.13.2.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
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Figure 4.12 Ring currents (dotted lines) induced by an external magnetic field B0 induce magnetic fields in
benzene, which add to the external field outside the ring and oppose it inside, above and below.
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Figure 4.13 Regions of effective shielding (+) and deshielding (–) in ethyne (a) and ethene (b).
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
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Figure 4.14 Some typical ranges and some representative examples of 13C chemical shifts.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
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Figure 4.15 (a) Dependence of the reduced shielding constant * (which is the shielding constant s divided
by 0, the value when the atom under consideration is surrounded by four non-polar bonds) on the atomic
charge for compounds containing four-coordinate atoms C (- - - - line), Si (— line), and Ge, Sn and Pb (-·-·line). Reprinted with permission from [12]. Copyright 1975 Oldenbourg Verlag. (b) Dependence of 31P NMR
chemical shifts on the degree of substitution of Cl and Br atoms by F atoms. Redrawn with permission from
[13]. Copyright 1968 Taylor & Francis.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Figure 4.16 Structures of the nine isomers of WFnCl6-n (n = to 6).
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
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Figure 4.17 Representation of 31P chemical shifts of phosphines with H, SiH3 and PF2 substituents. The
regularity of changes enables the chemical shifts of the unknown compounds P(PF2)3, PH(PF2)2 and
P(PF2)2(SiH3) to be predicted.
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Figure 4.18 Correlation between chemical shifts of analogous selenium and tellurium compounds.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
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Figure 4.19
31
P NMR spectra of the phosphorus(III) halides (a) PCl3, (b) PFCl2, (c) PF2Cl and (d) PF3.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
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Figure 4.20 Energy-level diagram for two spin-1/2 nuclei A and X (a) with no interaction (coupling constant
JAX = 0) and with interaction by (b) a positive and (c) a negative coupling constant. Below are the schematic
spectra that would be observed.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
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Figure 4.21 Coupling patterns derived by considering stepwise splitting of a resonance by coupling to more
and more spin-1/2 nuclei. The small vertical bars indicate the intensity distribution. Three splittings of the
same magnitude lead to a quartet for the PF3 case.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
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Figure 4.22 Coupling pattern derived by considering stepwise splitting of a resonance by two couplings to
spin-1/2 nuclei of the same magnitude (P–F) and one of a different magnitude (P–H), leading to a triplet of
doublets for the PF2H case.
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Figure 4.23 Typical Pascal’s triangle multiplet patterns. (a) P NMR spectrum of P(OCH3)3 with a decet
11
splitting and (b) B NMR spectrum of K[B(CF3)4] with a tridecet splitting. In the second case magnified views
of the outermost lines of the 13-line pattern are also shown, because the ratio in intensity between the
outermost lines and the central line is 1:924. The weak lines between the strong ones, marked with asterisks,
13
arise from coupling to C, present in 1% natural abundance. Spectrum (b) redrawn with permission from
[19]. Copyright 2001 John Wiley and Sons.
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15
Figure 4.24 PNMR spectrum of PF2H ( NH2)2. It is a doublet (JPH) of triplets (JPF) of triplets (JPN) of
quintets (JPH) – 90 lines in all.
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Figure 4.25 H NMR spectrum of disilane, Si2H6.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Figure 4.26
13
C NMR spectrum of [Pt3(CNCMe3)6] with coupling to hydrogen atoms suppressed.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
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Figure 4.27 15N NMR spectrum of a cyclic silylamine (recorded in 1H-decoupled DEPT mode, explained in
Section 4.12.2).
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
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Figure 4.28 13C NMR spectrum with proton decoupling of an allyl palladium complex.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Figure 4.29 1H NMR spectrum of the residual protons in a sample of deuterated toluene. Insets: natural
abundance 2H NMR spectrum of normal toluene.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Figure 4.30 (a) 1H NMR spectrum of GeH4; the ten evenly spaced lines are due to the 8% of molecules that
contain 73Ge (I = 9/2); the intense central line (cut) arises from all other isotopic species. (b) 19F NMR
9
spectrum of hexafluorobromate(V), BrF6 ; due to the presence of the two bromine isotopes 7 Br (50.7%, I =
3/2) and 81Br (49.4%, I = 3/2) there are two 1:1:1:1- quartet patterns with two coupling constants; their outer
lines are resolved, the inner lines overlap. Redrawn from [22]. Copyright Wiley-VCH Verlag GmbH & Co.
KGaA.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
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Figure 4.31 Calculated band shapes for spectra of a spin-1/2 nucleus (1H) coupled to a spin-1 nucleus (14N).
The shape depends on the ratio of 14N relaxation rate to the NH coupling. For very fast relaxation just a
single line is observed, while for slow relaxation there are three lines of equal intensity.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
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Figure 4.32 73Ge NMR spectrum (I = 9/2) of (a) Ph3GeH and (b) PhGeH3 with doublet and quartet splittings
(1JGeH = 98 Hz in both cases).
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
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19
1
Figure 4.33 F NMR spectrum of K[B(CF3)4], with a 1:1:1:1 quartet splitting due to a 2J(19F 1B) coupling and
a septet of smaller intensity due to 2J(19F10B); two lines of the septet are hidden behind those of the quartet.
Note that the chemical shifts of the two multiplets are not exactly the same. Redrawn with permission from
[19]. Copyright 2001 John Wiley and Sons.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Figure 4.34 Empirical relation between the value of the 1J(29Si15N) coupling constant and the Si–N distance
observed by crystal structure determination [21]. Reprinted from [21]. Copyright Wiley-VCH Verlag GmbH &
Co. KGaA.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
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Figure 4.35 (a) Definition of the torsion angle τ. (b) Karplus curve (range) for the dependence of 3J(1H1H) on
the torsion angle τ in H-C-C-H systems. (c) Karplus curve for 3J(119Sn1H) in 1-(trimethylstannyl) propane
based on calculated and experimental data. The fitted function is 3J(τ) = –42.77 + 8.87 cos() –43.9 cos(2τ).
Redrawn with permission from [24]. Copyright 2009 John Wiley and Sons.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Figure 4.36 (a) 1H NMR spectrum of the borane adduct (HF4C6)3BPMe3 with a triplet of triplets of doublets
splitting pattern, attributed to 6JHP, 3JHF and 4JHF couplings. (b) 1H NMR spectrum of the borane adduct
(HF4C6)3BPEt3 after application of 4 bar of H2 gas, showing the formation of the hydridoborate [(HF4C6)3B] ‾
+
[HPEt3] . Only the aryl regions of the spectra are shown. Adapted with permission from [27]. Copyright 2010
American Chemical Society.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Figure 4.37 1H-decoupled NMR spectra of the bis-phosphine in CDCl3: (a) 31P NMR spectrum; (b) 19F NMR
spectrum. Both spectra consist primarily of two doublets, due to two chemically inequivalent nuclei coupling
with one another [2JFF in (b) and 5JPP in (a)]. In addition, the high-frequency 31P resonance and the lowfrequency 19F resonance show 31P19F coupling through space of 2.3 Hz. Note that in each case the outer
lines are less intense than the inner lines; this is a second-order effect. Adapted with permission from [28].
Copyright 2011 John Wiley and Sons.
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Figure 4.38 1H NMR spectra of CH3CH2SPF2. The 360MHz spectrum (a) is first-order, but the 80MHz
spectrum (b) is second-order, and not easy to interpret. The CH2 resonances in spectrum (a) are a doublet
(3JPH) of quartets (3JHH) of triplets (4JFH) and the CH3 resonances are a triplet (3JHH) of triplets (3JFH).
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
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Figure 4.39 19F NMR spectrum of S(PF2)2. The spectrum is centrosymmetric and half of the total intensity
falls in the two most intense lines, which are truncated in the figure.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
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Figure 4.40 Resonances from the SiH3 protons in the 1H NMR spectrum of F2P15NHSiH3. The pattern is a
doublet of doublets of doublets of triplets, but because of the relationships between coupling constants many
lines overlap: 3 JPH = 8, 3JHH = 4, 2JNH = 3, 4JFH = 2 Hz, approximately.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
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Figure 4.41 7Li, 31P and 119Sn NMR spectra of three species detected in solutions of tributylstannyllithium in
diethyl ether that were titrated with HMPA at low temperatures. Adapted with permission from [32]. Copyright
1994 American Chemical Society.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Figure 4.42 (a) 31P NMR spectrum of Me3P=C(SiH2Ph)2 recorded without decoupling. (b) Selectively
decoupled 31P NMR spectrum of a mixture of the ylids Me3P=C(SiH2Ph)(SiH(Ph)SeSiH2Ph) and
Me3P=C(SiH2Ph)2; the resonance frequencies of the methyl groups at phosphorus (marked ) were
selectively radiated.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
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Figure 4.43 Schematic pulse sequences for (a) a broad-band decoupling experiment, in which the X nucleus
is irradiated during the time of recording the FID, and (b) a variant using a series of composite 180° pulses
instead of broad-band decoupling.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
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Figure 4.44 11B NMR spectra of B10H14, 4.I, (a) without and (b) with 11B decoupling.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
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Figure 4.45 1H NMR spectrum of F2P15NHSiH3 with 15N decoupling (1H{15N}). This spectrum should be
compared with that shown in Figure 4.40, which was recorded without decoupling.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
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Figure 4.46 (a) Proton decoupled and (b) coupled 29Si NMR spectra of triphenylsilane, HSiPh3. Reproduced
with permission from [35]. Copyright 1975 Taylor & Francis.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Figure 4.47 Experimental sequences for (a) gated decoupling and (b) inverse gated decoupling experiments.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Figure 4.48 (a) The INEPT pulse sequence for the example 15N{1H}. (b) The [AX] spin system 1H15N in its
equilibrium state of population. (ОО and  represent the populations of H and N states, respectively.) The
two spectra show schematically how the spectra would look if direct observation (single 90° pulse) was
attempted. (c) Selective inversion in the proton transition creates a non-equilibrium population in the [AX]
spin system, after which the X nuclei can be observed with increased intensity I.
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15
2
Figure 4.49 An N INEPT experiment for tris (phenylsilyl) hydrazine. A JNH coupling was used in the INEPT
1
pulse sequence. The much larger JNH (83Hz) splitting into a doublet of the resonance at -325 ppm is
2
2
3
undistorted, while the JNH coupling pattern has a phase inversion (triplet, JNSiH = 6:0 Hz, of quintets, JNNSiH
= 2:0 Hz). Knowing this, it is not difficult to see the quintet pattern (shown as a stick diagram) for the
2
resonance at 330.2 ppm due to a JNSiH coupling (6.1Hz), which is further split into a doublet of triplets with
2
3
equal coupling constants of 1.2 Hz ( JNNH and JNNSiH).
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1
Figure 4.50 3C NMR spectra of the palladium complex whose structure is displayed, showing the
resonances of (a) CH3 groups, (b) CH2 groups, (c) CH groups and (d) quarternary carbon atoms only.
Spectra (a), (b) and (c) were obtained using variants of the DEPT pulse sequence, followed by linear
combination of the three original DEPT spectra.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
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Figure 4.51 Pulse sequence of the COSY experiment.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Figure 4.52 (a) A set of FIDs recorded with increasing delay time t1 for a 2D spectrum. (b) Fourier
transformation in the time domain t2 results in a series of 1D NMR spectra. (c) A second Fourier
transformation of the spectra in the time domain t1 results in a 2D spectrum, here drawn as a stack plot, of
one signal.
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Figure 4.53 11B-COSY NMR spectrum for B10H14, 4.I. The 1D spectra at the sides are the 1H-coupled B
NMR spectrum, with all peaks showing a doublet splitting for the BH units.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Figure 4.54 2D COSY 183W NMR spectrum of the heteropolytungstate anion a1-[P2W17O61] 0–; the
assignment is given above the top 1D projection and corresponds to the numbering in the polyhedral
representation shown on the right (tungsten atoms within O6 octahedra). The gray lines in the structure
indicate anticipated very strong (thick lines, 20–30 Hz) or weak (dashed lines, <10 Hz, not observed as cross
peaks) 2JWW couplings between the tungsten nuclei around the vacant site. Reproduced with permission from
[38]. Copyright 2006 American Chemical Society.
1
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
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Figure 4.55 One-dimensional row slices of the 2D TOCSY spectrum of the mixture of isomers of the
ferrocene derivatives shown and labeling of the protons forming the four spin systems. Reproduced with
permission from [39]. Copyright 1998 American Chemical Society.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
1
Figure 4.56 Heteronuclear 2D 1H11B correlation spectra for B10H14, 4.I. Spectrum (a) is a classical 1H 1BHETCOR spectrum, and spectrum. Adapted from [40]. Copyright 1984, with permission from Elsevier.
Spectrum (b) is a 1H11B-HMQC, which uses polarization transfer and is much quicker to perform, but
essentially contains the same information. Courtesy of Dr Andreas Mix, University of Bielefeld.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Figure 4.57 (a) HMQC and (b) HSQC 2D 31P89Y{1H} correlation spectra for a ca. 0.14M solution of 1:1
Y(NO3)3·6H2O and Ph3PO in THF, measured at 60 °C. It took ca. 6 h to record these spectra. Reproduced
from [42] with permission of The Royal Society of Chemistry.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Figure 4.58 31P89Y{1H} HSQC-f1-coupled spectra of mixtures of Ph3PO and Y(NO3)3·6H2O measured at –60
°C in dilute solution in THF. (a) Ph3PO/Y(NO3)3.6H2O in a 1:1 molar ratio. (b) Ph3PO/Y(NO3)3·6H2O in a 1:
0.3 molar ratio. Reproduced from [42] with permission of The Royal Society of Chemistry.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Figure 4.59 Long-range 1H13C correlation (HMBC) spectrum of a salicylaldoximato tin complex. Only the
high-frequency range of 1H is shown, as this was used to assign the OH-group signals. Reproduced with
permission from [43]. Copyright 1996 American Chemical Society.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Figure 4.60 Heteronuclear 2D 1H6Li Nuclear Overhauser Effect (HOESY) spectrum for the
tetramethylethylenediamine adduct of 2-lithio-1-phenylpyrrole. Reproduced with permission from [44].
Copyright Wiley-VCH Verlag GmbH & Co. KGaA.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Figure 4.61 (a) Heteronuclear 2D 1H19F Nuclear Overhauser Effect (HOESY) spectrum of [h10-{Me2Si(h5C5H4)2}Zr(CH3) {m-(CH3)B(C6F5)3}]. Outside the box are the high-resolution 1D NMR spectra, and inside is
the projection of the 2D spectrum onto the 1H axis. (b) Homonuclear 2D 1H1H NOESY spectrum. Adapted
with permission from [45]. Copyright 2004 American Chemical Society.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Figure 4.62 (a) Stack plot of the DOSY NMR spectra for a solution of h -(C5Me5)SiN(SiMe3)2 (4.XXVI); the
high-frequency signal corresponds to C6H5, the low-frequency signal to the SiMe3 groups. (b) Plot of relative
intensity of the C6H5-signals (I/I0) versus the field gradient strength. The plot for the Me3Si-signals is very
similar. Courtesy of Dr Andreas Mix, University of Bielefeld.
1
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Figure 4.63 (a) Asymmetric unit of the crystal structure of tetramethyldiphosphine disulfide,
Me2P(S)P(S)Me2. (b)–(d) 31P CP NMR spectra (CP is explained on p. 144) of a single crystal of
tetramethyldiphosphine disulfide for stepwise changed rotations of the crystal about its x, y, and z axes,
acquired at 4.7 T. (e) Spectrum taken at a y rotation of 36° (marked in (c) by two arrows). Peaks marked #
are assigned to P(1) and P(1A) and those marked to * P(2) and P(3). Adapted with permission from [55].
Copyright 2000 American Chemical Society.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Figure 4.64 19F NMR spectra of KAsF6, with and without magic angle spinning.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Figure 4.65 Schematic representation of the magic angle about which the sample is spun in MAS NMR
spectroscopy.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Figure 4.66 (a) 31P CP NMR spectra of a static powder sample of tetramethyldiphosphine disulfide,
Me2P(S)P(S)Me2, measured at two different field strengths, 4.7 and 9.7 T. (b) and (c) 31P CP-MAS NMR
spectra of a sample, measured at two different field strengths and spinning rates. The inset in (b) is an
expansion of the signal group indicated by the arrow, which is also the center band. Note that the ppm scale
applies only to (c) and not to (b). Adapted with permission from [55]. Copyright 2000 American Chemical
Society.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Figure 4.67 Solid-state CP-MAS NMR spectra of [Ag(NH3)2]NO3. (a) 15N NMR spectrum recorded at 3.5 kHz
spinning rate. Inset is an expansion of the signals at low frequencies. Reprinted with permission from [58a].
109
Copyright 2004 John Wiley and Sons. (b) Center-band of the Ag NMR spectrum recorded at 4.0 kHz
spinning rate. Reprinted with permission from [58a]. Copyright 2004 John Wiley and Sons. (c) Crystal
structure of [Ag(NH3)2]NO3 (H atoms not shown, redrawn from [58(b)].
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Figure 4.68 31P MAS NMR spectra of powder samples of (a) [Cl3In{P(p-anis)3}2] and (b) [Cl3In{P(m-anis)3}2].
Redrawn with permission from [59]. Copyright 2010 American Chemical Society.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Figure 4.69 1H NMR spectra of the SiH resonances of enantiomers (a) and (b) of a bicyclic
tetrasilylhydrazine at various temperatures between –80 and –20 °C. Reproduced with permission from
[63]. Copyright 1993 American Chemical Society.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Figure 4.70 (a) 19F NMR spectra of Cp(OC)2Re(h2-C6F6) at variable temperatures. (b) Definition of full width
at half height. Reprinted by kind permission of Prof Robin N. Perutz, York.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Figure 4.71 2D 31P EXSY spectrum of the rhodium complex measured at 300 K. Reproduced with
permission from [67]. Copyright 2008 American Chemical Society.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Figure 4.72 Addition of successively increasing amounts of the bases DMP, DMMP and DMSO to the adduct
of the bis-Lewis acid [o-C6F4(HgCl)2] with acetone, as observed by 199Hg NMR spectroscopy.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Figure 4.73 Diffusion coefficients of 1HNMRresonances observed by the DOSY method for the reaction of
the bis-Lewis acid 1,8-bis (diethylgallanylethynyl) anthracene with pyridine. Courtesy of Jan-Hendrik Lamm,
University of Bielefeld [69].
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Figure 4.74 (a) 19F NMR and (b) 9Be NMR spectra of an aqueous solution of Be2+ with various
concentrations of fluoride. Note that the 9Be NMR spectra are superpositions of signals of the different
2+
species that can be identified in the 19F NMR, plus [Be(H2O)4] . In discussion problem 4.49 you are asked to
analyze the 9Be spectra in detail.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Figure 4.75 (a) 7Li NMR spectra, (b) graphs of concentrations versus time and (c) kinetic scheme derived
from an RINMR study of the reactions of n-butyl lithium with trimethylsilylacetylene. Reproduced with
permission from [72]. Copyright 2007 American Chemical Society.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Figure 4.76 (a) Principle of function of the two-chamber NMR tube: (left) closed mode, (right) after lifting the
5
insert. Reproduced with permission from [73]. Copyright 2010 American Chemical Society. (b) Reaction of [(h Me5C5)Si][B(C6F5)4] with LiC5H5 leading to an instable product, as was studied with the device shown in (a).
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Figure 4.77 (a) 31P{1H} decoupled NMR spectrum of the ruthenium complex showing two [AB] sub-spectra.
(b) 31P{1H} decoupled NMR spectrum of the same complex after undergoing a one-electron oxidation.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Figure 4.78 27Al NMR spectra of a range of compounds of the formula [M(AlMe4)3], with M = La, Nd, Pr, Sm,
Yand Lu. Redrawn with permission from [41a]. Copyright 2007 John Wiley & Sons.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Figure 4.79 1H NMR spectra of the tris-dimethyldi(phenylethynyl)aluminates of La, Pr, Sm, Ho and Tm. An
assignment of the protons is provided in the structure. The insets marked with * represent the regions
between 5 and 8 ppm, ‘solv’ denotes the position of the solvent signal (C6H6). The data and drawing were
kindly provided by Anja Nieland and Dr Andreas Mix, University of Bielefeld [75].
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Figure 4.80 1H-decoupled NMR spectrum of the oxidized iron(III) cytochrome b2, the central part of which is
shown as the structure in the inset. Intense peaks marked v, m and p have been assigned to protons that are
part of vinyl, methyl and propionate substituents on the porphyrin.
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Figure 4.I
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Figure 4.II
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Figure 4.III
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Figure 4.IV
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Figure 4.V to 4.VII
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Figure 4.VIII to 4.IX
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Figure 4.X to 4.XIII
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Figure 4.XIV to 4.XX
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Figure 4.XXI
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Figure 4.XXII - XXIV
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Figure 4.XXV
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Figure 4. XXVI and XXVII
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Figure 4. XXVIII
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Figure 4. XXIX
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Review Question Figure 4.4
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Discussion Problem Figure 4.32
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Discussion Problem Figure 4.33
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Discussion Problem Figure 4.41
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Discussion Problem Figure 4.43
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Discussion Problem Figure 4.45
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.
Discussion Problem Figure 4.44
Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison
@ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.