Direct coupling constants, carbon

Direct coupling constants have been measured between carbon and the following metals or metalloids " Li, Si, V, Fe, Co, Ge,... 

For molecules dissolved in a nematic thermotropic liquid-crystal, the direct coupling constants can be determined and from these the molecular geometry can be calculated. If the satellites are determined, not only the proton structure but the carbon skeleton of the molecule can be established. Oxirane has been measured in two laboratories. It proved possible to determine the orientation, the sign of the indirect coupling constant, and the geometry. Enantiomers can readily be determined by recording measurements in optically active liquid-crystals as solvents. ... 

Take note that this effect would stabilize the equatorial anomers, hence diminishes the anomeric effect of oxygenated substituents. However, there are other physical indications of the favoured delocalization of the cyclic oxygen towards the exocyclic oxygen as furnished by the direct coupling constant value Vch between the anomeric carbon and hydrogen. A comparison of the 7ch values, measured on about 20 anomeric pairs having various configurations and substitutions, shows that for each pair we observe... 

Spin densities help to predict the observed coupling constants in electron spin resonance (ESR) spectroscopy. From spin density plots you can predict a direct relationship between the spin density on a carbon atom and the coupling constant associated with an adjacent hydrogen. 

The delay is generally kept at Vi x> The coupling constant Jcc for direcdy attached carbons is usually between 30 and 70 Hz. The first two pulses and delays (90J -t-180 2-t) create a spin echo, which is subjected to a second 90J pulse (i.e., the second pulse in the pulse sequence), which then creates a double-quantum coherence for all directly attached C nuclei. Following this is an incremented evolution period tu during which the double quantum-coherence evolves. The double-quantum coherence is then converted to detectable magnetization by a third pulse 0,, 2, and the resulting FID is collected. The most efficient conversion of double-quantum coherence can... 

Rotational-echo double-resonance (REDOR)(75,79) is a new solid-state NMR technique which is sensitive to through-space carbon-nitrogen interactions between selectively 13C and 15N-enriched sites separated by up to 5A (20-22). The parameter directly measured in a REDOR experiment is the heteronuclear dipolar coupling constant DCN, which is in itself proportional to the inverse third power of the intemuclear distance, rCN. It is this dependence on (icn)3 which accounts both for REDOR s ability to accurately measure short distances and its insensitivity to longer-range interactions. As a technique which can probe, in detail, intermolecular interactions over a distance range of 5A, REDOR is well suited to studying the distribution of small selectively-labeled molecules in polymer delivery systems. 

Again, we need to define a coupling constant J to set up this experiment. Here for optimum sensitivity we have used an average value for direct (one-bond) carbon-hydrogen coupling constants of 160 Hz. This choice works well for most CH bonds, but is rather low if an acetylenic CH bond is present. 

Fig. 10.18. IDR (Inverted Direct Response)—HSQC-TOCSY pulse sequence. The experiment first uses an HSQC sequence to label protons with the chemical shift of their directly bound carbons, followed by an isotropic mixing period that propagates magnetization to vicinal neighbor and more distant protons. The extent to which magnetization is propagated in the experiment is a function of both the size of the intervening vicinal coupling constants and the duration of the mixing period. After isotropic mixing, direct responses are inverted by the experiment and proton detection begins.

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