Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. 2013 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 4.1 (a) Precession of the angular momentum of a nucleus about the magnetic field axis. The double- headed 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.

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 4.2 (a) Linear dependence of the splitting of energy levels with the applied magnetic field. (b) Energy- level 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 @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. 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 @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. 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 @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 4.5 (a) Magnetization of the sample M 0 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 M y in the y´ direction. (c) The result of a 90 o pulse in the x´ direction is full magnetization in the y´ direction. (d) The result of a 180 o 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 @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 4.6 (a) Magnetization M 0 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 M y 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 180 o pulse.

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 4.7 Relaxation of the transverse magnetization M y ´ 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 @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 4.8 Schematic illustration of the dependence of the relaxation times T 1 and T 2 on the molecular tumbling rates, expressed in terms of reciprocal correlation time T -–1 c.

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 4.9 (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 @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. 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 @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 4.11 11 B NMR spectrum of B 10 H 14. All couplings to hydrogen were removed. The boron cage structure is as shown, so four equivalent (B 5, B 7, B 8 and B 10 ) 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 @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 4.12 Ring currents (dotted lines) induced by an external magnetic field B 0 induce magnetic fields in benzene, which add to the external field outside the ring and oppose it inside, above and below.

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 4.13 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 @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 4.14 Some typical ranges and some representative examples of 13 C chemical shifts.

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 4.15 (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 31 P 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 WF n Cl 6-n (n = to 6).

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 4.17 Representation of 31 P chemical shifts of phosphines with H, SiH 3 and PF 2 substituents. The regularity of changes enables the chemical shifts of the unknown compounds P(PF 2 ) 3, PH(PF 2 ) 2 and P(PF 2 ) 2 (SiH 3 ) to be predicted.

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 4.18 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 @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 4.19 31 P NMR spectra of the phosphorus(III) halides (a) PCl 3, (b) PFCl 2, (c) PF2Cl and (d) PF 3.

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 4.20 Energy-level diagram for two spin-1/2 nuclei A and X (a) with no interaction (coupling constant J AX = 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 @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. 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 PF 3 case.

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 4.22 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 PF 2 H case.

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 4.23 Typical Pascal’s triangle multiplet patterns. (a) 31 P NMR spectrum of P(OCH 3 ) 3 with a decet splitting and (b) 11 B NMR spectrum of K[B(CF 3 ) 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, arise from coupling to 13 C, present in 1% natural abundance. Spectrum (b) 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 4.24 31 PNMR spectrum of PF 2 H ( 15 NH 2 ) 2. It is a doublet (J PH ) of triplets (J PF ) of triplets (J PN ) of quintets (J PH ) – 90 lines in all.

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 4.25 1 H NMR spectrum of disilane, Si 2 H 6.

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 [Pt 3 (CNCMe 3 ) 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 @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 4.27 15 N NMR spectrum of a cyclic silylamine (recorded in 1 H-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 @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 4.28 13 C 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 1 H NMR spectrum of the residual protons in a sample of deuterated toluene. Insets: natural abundance 2 H 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) 1 H NMR spectrum of GeH 4 ; the ten evenly spaced lines are due to the 8% of molecules that contain 73 Ge (I = 9/2); the intense central line (cut) arises from all other isotopic species. (b) 19 F NMR spectrum of hexafluorobromate(V), BrF 6 - ; due to the presence of the two bromine isotopes 7 9 Br (50.7%, I = 3/2) and 81 Br (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 @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 4.31 Calculated band shapes for spectra of a spin-1/2 nucleus ( 1 H) coupled to a spin-1 nucleus ( 14 N). The shape depends on the ratio of 14 N 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 @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 4.32 73 Ge NMR spectrum (I = 9/2) of (a) Ph 3 GeH and (b) PhGeH 3 with doublet and quartet splittings ( 1 J GeH = 98 Hz in both cases).

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 4.33 19 F NMR spectrum of K[B(CF 3 ) 4 ], with a 1:1:1:1 quartet splitting due to a 2 J( 19 F 1 1 B) coupling and a septet of smaller intensity due to 2 J( 19 F 10 B); 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 1 J( 29 Si 15 N) 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 @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 4.35 (a) Definition of the torsion angle τ. (b) Karplus curve (range) for the dependence of 3 J( 1 H 1 H) on the torsion angle τ in H-C-C-H systems. (c) Karplus curve for 3 J( 119 Sn 1 H) in 1-(trimethylstannyl) propane based on calculated and experimental data. The fitted function is 3 J( τ ) = –42.77 + 8.87 cos(  ) –43.9 cos(2 τ ). 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) 1 H NMR spectrum of the borane adduct (HF 4 C 6 ) 3 BPMe 3 with a triplet of triplets of doublets splitting pattern, attributed to 6 J HP, 3 J HF and 4 J HF couplings. (b) 1 H NMR spectrum of the borane adduct (HF 4 C 6 ) 3 BPEt 3 after application of 4 bar of H 2 gas, showing the formation of the hydridoborate [(HF 4 C 6 ) 3 B] ‾ [HPEt 3 ] +. 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 1 H-decoupled NMR spectra of the bis-phosphine in CDCl 3 : (a) 31 P NMR spectrum; (b) 19 F NMR spectrum. Both spectra consist primarily of two doublets, due to two chemically inequivalent nuclei coupling with one another [ 2 J FF in (b) and 5 J PP in (a)]. In addition, the high-frequency 31 P resonance and the low- frequency 19 F resonance show 31 P 19 F 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.

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 4.38 1 H NMR spectra of CH 3 CH 2 SPF 2. The 360MHz spectrum (a) is first-order, but the 80MHz spectrum (b) is second-order, and not easy to interpret. The CH 2 resonances in spectrum (a) are a doublet ( 3 J PH ) of quartets ( 3 J HH ) of triplets ( 4 J FH ) and the CH 3 resonances are a triplet ( 3 J HH ) of triplets ( 3 J FH ).

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 4.39 19 F NMR spectrum of S(PF 2 ) 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 @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 4.40 Resonances from the SiH 3 protons in the 1 H NMR spectrum of F 2 P 15 NHSiH 3. The pattern is a doublet of doublets of doublets of triplets, but because of the relationships between coupling constants many lines overlap: 3 J PH = 8, 3 J HH = 4, 2 J NH = 3, 4 J FH = 2 Hz, approximately.

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 4.41 7 Li, 31 P and 119 Sn 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) 31 P NMR spectrum of Me 3 P=C(SiH 2 Ph) 2 recorded without decoupling. (b) Selectively decoupled 31 P NMR spectrum of a mixture of the ylids Me 3 P=C(SiH 2 Ph)(SiH(Ph)SeSiH 2 Ph) and Me 3 P=C(SiH 2 Ph) 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 @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. 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 @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 4.44 11 B NMR spectra of B 10 H 14, 4.I, (a) without and (b) with 11 B decoupling.

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 4.45 1 H NMR spectrum of F 2 P 15 NHSiH 3 with 15N decoupling ( 1 H{ 15 N}). 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 @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 4.46 (a) Proton decoupled and (b) coupled 29 Si NMR spectra of triphenylsilane, HSiPh 3. 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 15 N{ 1 H}. (b) The [AX] spin system 1 H 15 N 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.

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 4.49 An 15 N INEPT experiment for tris (phenylsilyl) hydrazine. A 2 J NH coupling was used in the INEPT pulse sequence. The much larger 1 J NH (83Hz) splitting into a doublet of the resonance at -325 ppm is undistorted, while the 2 J NH coupling pattern has a phase inversion (triplet, 2 J NSiH = 6:0 H z, of quintets, 3 J NNSiH = 2:0 Hz). Knowing this, it is not difficult to see the quintet pattern (shown as a stick diagram) for the resonance at 330.2 ppm due to a 2 J NSiH coupling (6.1Hz), which is further split into a doublet of triplets with equal coupling constants of 1.2 Hz ( 2 J NNH and 3 J NNSiH ).

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 4.50 1 3 C NMR spectra of the palladium complex whose structure is displayed, showing the resonances of (a) CH 3 groups, (b) CH 2 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 @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. 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 t 1 for a 2D spectrum. (b) Fourier transformation in the time domain t 2 results in a series of 1D NMR spectra. (c) A second Fourier transformation of the spectra in the time domain t 1 results in a 2D spectrum, here drawn as a stack plot, of one signal.

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 4.53 11 B-COSY NMR spectrum for B 10 H 14, 4.I. The 1D spectra at the sides are the 1 H-coupled 11 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 183 W NMR spectrum of the heteropolytungstate anion  1 -[P 2 W 17 O 61 ] 1 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 O 6 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) 2 J WW couplings between the tungsten nuclei around the vacant site. Reproduced with permission from [38]. Copyright 2006 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 4.55 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. Figure 4.56 Heteronuclear 2D 1 H 11 B correlation spectra for B 10 H 14, 4.I. Spectrum (a) is a classical 1 H 1 1 B- HETCOR spectrum, and spectrum. Adapted from [40]. Copyright 1984, with permission from Elsevier. Spectrum (b) is a 1 H 11 B-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 31 P 89 Y{ 1 H} correlation spectra for a ca. 0.14M solution of 1:1 Y(NO 3 ) 3· 6H 2 O and Ph 3 PO 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 31 P 89 Y{1H} HSQC-f 1 -coupled spectra of mixtures of Ph 3 PO and Y(NO 3 ) 3· 6H 2 O measured at –60 °C in dilute solution in THF. (a) Ph 3 PO/Y(NO 3 ) 3.6H 2 O in a 1:1 molar ratio. (b) Ph 3 PO/Y(NO 3 ) 3· 6H 2 O in a 1: 0.3 molar ratio. Reproduced from [42] with permission of The Royal Society of Chemistry. o

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 1 H 13 C correlation (HMBC) spectrum of a salicylaldoximato tin complex. Only the high-frequency range of 1 H 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 1 H 6 Li 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 1 H 19 F Nuclear Overhauser Effect (HOESY) spectrum of [  10 -{Me 2 Si(  5 - C 5 H 4 ) 2 }Zr(CH 3 ) {  -(CH 3 )B(C 6 F 5 ) 3 }]. Outside the box are the high-resolution 1D NMR spectra, and inside is the projection of the 2D spectrum onto the 1 H axis. (b) Homonuclear 2D 1 H 1 H 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  1 -(C 5 Me 5 )SiN(SiMe 3 ) 2 (4.XXVI); the high-frequency signal corresponds to C 6 H 5, the low-frequency signal to the SiMe 3 groups. (b) Plot of relative intensity of the C 6 H 5 -signals (I/I 0 ) versus the field gradient strength. The plot for the Me 3 Si-signals is very similar. 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 4.63 (a) Asymmetric unit of the crystal structure of tetramethyldiphosphine disulfide, Me 2 P(S)P(S)Me 2. (b)–(d) 31 P 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 19 F NMR spectra of KAsF 6, 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) 31 P CP NMR spectra of a static powder sample of tetramethyldiphosphine disulfide, Me 2 P(S)P(S)Me 2, measured at two different field strengths, 4.7 and 9.7 T. (b) and (c) 31 P 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(NH 3 ) 2 ]NO 3. (a) 15 N NMR spectrum recorded at 3.5 kHz spinning rate. Inset is an expansion of the signals at low frequencies. Reprinted with permission from [58a]. Copyright 2004 John Wiley and Sons. (b) Center-band of the 109 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(NH 3 ) 2 ]NO 3 (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 31 P MAS NMR spectra of powder samples of (a) [Cl 3 In{P(p-anis) 3 } 2 ] and (b) [Cl 3 In{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 1 H 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) 19 F NMR spectra of Cp(OC) 2 Re(  2 -C 6 F 6 ) 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 31 P 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-C 6 F 4 (HgCl) 2 ] with acetone, as observed by 199 Hg 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 1 HNMRresonances 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) 19 F NMR and (b) 9 Be NMR spectra of an aqueous solution of Be 2+ with various concentrations of fluoride. Note that the 9 Be NMR spectra are superpositions of signals of the different species that can be identified in the 19 F NMR, plus [Be(H 2 O) 4 ] 2+. In discussion problem 4.49 you are asked to analyze the 9 Be 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) 7 Li 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 insert. Reproduced with permission from [73]. Copyright 2010 American Chemical Society. (b) Reaction of [(  5 - Me 5 C 5 )Si][B(C 6 F 5 ) 4 ] with LiC 5 H 5 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) 31 P{ 1 H} decoupled NMR spectrum of the ruthenium complex showing two [AB] sub-spectra. (b) 31 P{ 1 H} 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 27 Al NMR spectra of a range of compounds of the formula [M(AlMe 4 ) 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 1 H 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 (C 6 H 6 ). 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 1 H-decoupled NMR spectrum of the oxidized iron(III) cytochrome b 2, 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. 2013 John Wiley & Sons,

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Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. 2013 John Wiley & Sons,

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