Details

Autor(en) / Beteiligte

• Abraham, Michael H.
• Buist, Gabriel J.
• Grellier, Priscilla L.
• McGill, R. Andrew
• Prior, David V.
• Oliver, Susan
• Turner, Elizabeth
• Morris, Jeffrey J.
• Taylor, Peter J.
• Nicolet, Pierre
• Maria, Pierre-Charles
• Gal, Jean-François
• Abboud, José-Luis M.
• Doherty, Ruth M.
• Kamlet, Mortimer J.
• Shuely, Wendel J.
• Taft, Robert W.

Titel

Hydrogen-bonding 8. Possible equivalence of solute and solvent scales of hydrogen-bond basicity of non-associated compounds

Ist Teil von

• Journal of physical organic chemistry, 1989-09, Vol.2 (7), p.540-552

Ort / Verlag

Sussex: John Wiley & Sons Ltd

Erscheinungsjahr

1989

Quelle

Wiley Online Library

Beschreibungen/Notizen

• Using the solvatochromic indicator method, a scale of solvent hydrogen‐bond basicity, β1 (General), has been set up using a series of double regression equations, \documentclass{article}\pagestyle{empty}\begin{document}$$ \nu = \nu _0 + s\pi _1^* + b\beta _1 $$\end{document} for 11 aniline‐type indicators. A similar solvent scale, β1 (Special), has been constructed by the homomorphic comparison method using only results by Laurence et al. on the indicators 4‐nitroaniline and 4‐nitro‐N,N‐dimethylaniline. Results are available from our previous work on a general solute scale, β 2H, and we have also obtained a special solute scale, β2 (pKHB) from available log K values for hydrogen‐bond complexation of bases with 4‐fluorophenol in CCl4. However, the two solute β2 scales are virtually identical. It is shown that there is a general connection between β1(General) and β 2H, with r = 0·9775 and s.d. = 0·05 for 32 compounds, and between β1(Special) and β 2H, with r = 0·9776 and s.d. = 0·06 for the same 32 compounds. The latter correlation over 60 compounds yields r = 0·9684 and s.d. = 0·07. However, there are so many compounds in these regressions for which the differences in the solvent and solute β values are larger than the total expected error of 0·07 units that the use of β1 to predict β2 or vice versa is a very hazardous procedure. About 70 new β1 values obtained by the double regression method are also reported.