13C-1H coupling

The one-bond 13C-1H couplings are dealt with in the next section. 

Table 19b 13C-1H Coupling Constants for the Furan Nucleus in Furocoumarins and Furochromones (Benzofuran...

Table 14 13C NMR chemical shifts (S, ppm from TMS) and one-bond 13C-1H coupling constants (Hz) of some simple heterocyclic cations (cf. pyridine, column 2)...

K. Bock and C. M. Pedersen, Two- and three-bond 13C—1H couplings in some carbohydrates, Acta... 

In cases of complexes bearing an exocyclic double bond directly coordinated to the metal center, the carbons of the double bond usually exhibit coupling with NMR-active metal centers and/or auxiliary ligands.6 14 18 19 The chemical shifts of the quaternary carbon atom vary from 66.976 to 82.2818 ppm, while the methylene group gives rise to signals at 29.16,14 41.91,6 or 51.3418 ppm in the 13C 1H NMR spectra. As one can see, the chemical shift variation is relatively broad and significantly affected by the nature of the metal center. 

The estimated correlation times for the loop domains of the order of 10 4 s are obtained for the suppressed peaks in the [l-13C]amino-acid-labelled bR, including Gly, Ala, and Leu residues as shown in Figure 24C. The loop dynamics can be also examined by measurements of the 13C-1H dipolar couplings by DIPSHIFT experiment in which fluctuations of the Co,-Cp vector result in additional motional averaging as order parameters, in addition to the rotation of Ala methyl groups which scales the dipolar... 

The best and easiest way to implement such an experiment is to use adiabatic inversion pulses, in order to introduce heterogeneity for evolution under 13C-1H scalar or residual dipolar couplings by means of a frequency-swept 180° pulse on 13C that inverts 13C nuclei at different positions in the NMR sample at different times (Figure 13) 40,45 This filter is robust with respect to pulse miscalibration and operates efficiently without the need to cycle the phases of pulses that otherwise is a common feature of non-destructive LPJFs. 

The DD-CSA cross-correlated relaxation, namely that between 13C-1H dipole and 31P-CSA, can also be used to determine backbone a and C angles in RNA [65]. The experiment requires oligonucleotides that are 13C-labeled in the sugar moiety. First, 1H-coupled, / - DQ//Q-II CP spectra are measured. DQ and ZQ spectra are obtained by linear combinations of four subspectra recorded for each q-increment. Then, the cross-relaxation rates are calculated from the peak intensity ratios of the doublets in the DQ and ZQ spectra. The observed cross-correlation rates depend on the relative orientations of CH dipoles with respect to the components of the 31P chemical shift tensor. As the components of the 31P chemical shift tensor in RNA are not known, the barium salt of diethyl phosphate was used as a model compound with the principal components values of -76 ppm, -16 ppm and 103 ppm, respectively [106]. Since the measured cross-correlation rates are a function of the angles / and e as well, these angles need to be determined independently using 3/(H, P) and 3/(C, P) coupling constants. 

As an example of the measurement of cross-correlated relaxation between CSA and dipolar couplings, we choose the J-resolved constant time experiment [30] (Fig. 7.26 a) that measures the cross-correlated relaxation of 1H,13C-dipolar coupling and 31P-chemical shift anisotropy to determine the phosphodiester backbone angles a and in RNA. Since 31P is not bound to NMR-active nuclei, NOE information for the backbone of RNA is sparse, and vicinal scalar coupling constants cannot be exploited. The cross-correlated relaxation rates can be obtained from the relative scaling (shown schematically in Fig. 7.19d) of the two submultiplet intensities derived from an H-coupled constant time spectrum of 13C,31P double- and zero-quantum coherence [DQC (double-quantum coherence) and ZQC (zero-quantum coherence), respectively]. These traces are shown in Fig. 7.26c. The desired cross-correlated relaxation rate can be extracted from the intensities of the cross peaks according to ... 

The size and orientation of the 31P CSA tensor have been calibrated from single-crystal solid state NMR data of barium diethylphosphate [31]. The projection angles 6CHa22 and i between the 1H,13C-dipolar coupling and the components of the 31P-CSA-tensor de-... 

Table 5 13C Chemical Shifts (S, p.p.m. from TMS) and One-bond l3C-1H Coupling Constants (Hz) of some Simple Heterocyclic Cations (cf. pyridine, column 1)...

Stereoselective aldol condensations provide a-substituted /J-hydroxycarbonyl compounds328, and it transpires that H- and 13C-NMR spectroscopy are excellent tools for determining their relative configurations. For example, it has been pointed out329 330 that the vicinal 1H,1H coupling constant is a good indicator of the stereochemistry (see Table 2)331 ... 

---