Hydrogen bonding scales

One of the most comprehensive hydrogen-bonding scales is due to Abraham and his coworkers50, who have derived the general solvation equation 651... 

In an atomic level simulation, the bond stretch vibrations are usually the fastest motions in the molecular dynamics of biomolecules, so the evolution of the stretch vibration is taken as the reference propagator with the smallest time step. The nonbonded interactions, including van der Waals and electrostatic forces, are the slowest varying interactions, and a much larger time-step may be used. The bending, torsion and hydrogen-bonding forces are treated as intermediate time-scale interactions. 

Table 1,5, Donor scales (Dg, DN and DNbulk) of some selected solvents, as well as acceptor number (AN) and hydrogen bond donor capacities (a).

Figure 4 shows the measured angle of 105° between the hydrogens and the direction of the dipole moment. The measured dipole moment of water is 1.844 debye (a debye unit is 3.336 x 10 ° C m). The dipole moment of water is responsible for its distinctive properties in the Hquid state. The O—H bond length within the H2O molecule is 0.96 x 10 ° m. Dipole—dipole interaction between two water molecules forms a hydrogen bond, which is electrostatic in nature. The lower part of Figure 4 (not to the same scale) shows the measured H-bond distance of 2.76 x 10 ° m or 0.276 nm. 

Attempts have also been made to separate non-specific effects of the local electrical field from hydrogen-bonding effects for a small group of ionic liquids through the use of the k scale of dipolarity/polarizability, the a scale of hydrogen bond donor acidity, and the (i scale of hydrogen bond basicity (see Table 3.5-1) [13, 16]. 

The interest in this area may be seen to stem from the biological area where the phenomenon is well known and accounts for the regularity in the structure of natural proteins and polynucleotides. Such polymers are efficiently synthesized by enzymes which arc capable of organizing monomer units within regularly structured molecular-scale spaces and exploiting weak forces such as hydrogen bonds and Van der Waal forces to control the polymerization process.. 

Other considerations aside, the use of dilute reagents minimizes effects of nonideality. This allows the use of concentrations in place of activities. Of course, the time scale, the sensitivity of the analytical method at different concentrations, and the use of other reaction components introduce additional considerations. Tied closely to this decision is the choice of solvent. Reaction rates may (or may not) be affected by such variables as polarity, dielectric constant, hydrogen-bonding ability, donor capacity, and viscosity. A change in solvent may change not only the rate but also the mechanism and possibly even the products. One cannot even assume that the net reaction is the... 

By comparing pKa and pKm values, Taft predicted the preferred sites for the hydrogen bond when two different functional groups are present and both may act as an acceptor for the hydrogen bond. Other applications of the p/CHB scale have also been described81. 

In the course of this study, the authors determined /Lvalues for dibenzyl, methyl phenyl, methyl p-nitrophenyl, di-p-tolyl, di-isopropyl and tetramethylene sulphoxides and for diethyl, dipropyl and dibutyl sulphites. The /Lscales are applied to the various reactions or the spectral measurements. The /Lscales have been divided into either family-dependent (FD) types, which means two or more compounds can share the same /Lscale, family-independent (FI) types. Consequently, a variety of /Lscales are now available for various families of the bases, including 29 aldehydes and ketones, 17 carboxylic amides and ureas, 14 carboxylic acids esters, 4 acyl halides, 5 nitriles, 10 ethers, 16 phosphine oxides, 12 sulphinyl compounds, 15 pyridines and pyrimidines, 16 sp3 hybridized amines and 10 alcohols. The enthalpies of formation of the hydrogen bond of 4-fluorophenol with both sulphoxides and phosphine oxides and related derivatives fit the empirical equation 18, where the standard deviation is y = 0.983. Several averaged scales are shown in Table 1588. 

A crystallographic scale of acidity has been developed. Measuring the mean C—H O distances in crystal structures correlated well with conventional P a(DMSO) values. An ab initio study was able to correlate ring strain in strained hydrocarbons with hydrogen-bond acidity. ... 

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