Baker–Nathan effect
In
This effect was described in 1935 by John W. Baker and W. S. Nathan.
The reaction is facilitated by electron-releasing substituents (the
A fundamental problem with the effect is that differences in the observed order are relatively small and therefore difficult to measure accurately. Other researchers have found similar results or very different results. An alternative explanation for the effect is differential solvation as orders invert on going from the solution phase to the gas phase.[5]
Today, the conjugation of neighbouring pi orbitals and polarised sigma bonds is known as hyperconjugation. Numerous anomalous physical measurements, including bond lengths and dipole moments, have been examined through this concept. The original formulation of the Baker-Nathan effect is no longer employed due to more logical reasons for rate accelerations in solutions and its historical context is discussed by Saltzman. [6]
References
- ^ HYPERCONJUGATION: INTERMEDIATES AND TRANSITION STATES IN REPLACEMENT AND ELIMINATION Peter B.D. de la Mare Pure Appl. Chem., Vol 56, No. 12, pp 755—1766, 1984 http://www.iupac.org/publications/pac/1984/pdf/5612x1755.pdf
- Bull. Hist. Chem.; 2012; 37(2); 82–90. {{http://acshist.scs.illinois.edu/bulletin_open_access/v37-2/v37-2%20p82-90.pdf}}