Deuterated solvents changing

Some species have a large number of exchangeable hydrogens. Thus, metal ions with many coordinated water molecules will become completely deuterated in D20. For example, Co(H20) + becomes Co(D20) +. If there were a 2 percent secondary kie per bond, it would be amplified to (1.02)12 or 1.27. It would not be a simple matter to demonstrate the operation of a primary kie in such a system because of this, given the p/f difference between the two metal ions and the general effects of the solvent change. 

The deuterium line of the deuterated solvent is used for this purpose, and, as stated earlier, the intensity of this lock signal is also employed to monitor the shimming process. The deuterium lock prevents any change in the static field or radiofrequency by maintaining a constant ratio between the two. This is achieved via a lock feedback loop (Fig. 1.10), which keeps a constant frequency of the deuterium signal. The deuterium line has a dispersion-mode shape i.e., its amplitude is zero at resonance (at its center), but it is positive and negative on either side (Fig. 1.11). If the receiver reference phase is adjusted correcdy, then the signal will be exactly on resonance. If, however, the field drifts in either direction, the detector will... 

Oxyanions also affect the coordination chemistry of the metal center (84). Molybdate and tungstate are tightly bound noncompetitive inhibitors (Ki s of ca. 4 (iM) (85). These anions bind to the reduced form of the enzyme, changing the rhombic EPR spectrum of the native enzyme to axial (Figure 1) and affecting the NMR shifts observed (84,85). Comparisons of the ENDOR spectra of reduced uterofenin and its molybdate complex show that molybdate binding causes the loss of iH features which are also lost when the reduced enzyme is placed in deuterated solvent (86). These observations suggest that molybdate displaces a bound water upon complexation. 

The Hammett p value for the following reaction is -4.8. Explain this in terms of a mechanism. If the reaction were carried out in deuterated solvent, would the rate change and would there be any deuterium incorporation into the product What is the silicon-containing product ... 

Proton NMR studies of N-methyl formamide (NMF) and NMA at high dilution in deuterated solvents have shown that the level of cis isomer of NMF is 8% in water, 10.3% in chloroform, 8.8% in benzene, and 9.2% in cyclohexane, while the level of cis-NMA (a model for the secondary peptide bond) is 1.5% in water and does not change very much in nonpolar solvents [18]. Ab initio molecular calculations suggest that the small difference in dipole moments in cis and trans forms explain the relative insensitivity of amides to solvent change, unlike esters [22,41], This may be explained by nearly identical free energies of solvation for the two isomers [18]. The energy difference between cis and trans isomers in aqueous solution (AG° = 2.5 kcal mol-1) accounts for the preferential trans conformation adopted by most peptide bonds. Similar results were obtained with nonproline tertiary amides [22]. 

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