New empirical models of substituent polarisability and their application to stabilisation effects in positively charged species
✍ Scribed by Johann Gasteiger; Michael G. Hutchings
- Publisher
- Elsevier Science
- Year
- 1983
- Tongue
- French
- Weight
- 205 KB
- Volume
- 24
- Category
- Article
- ISSN
- 0040-4039
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✦ Synopsis
Z?JO sirrple new models of substituent polarisability have been devised to take into account attenuation of substituent influence, and have been used to quantify electron retaxaz5on effects in core-ionised chlorine and nitrogen compounds, and relative stabilisation ofprotonated alkylamines. It has been realised that polarisability has a fundamental influence on chemical reactivity especially in the gas phase, as is well established,I but also in solution as demonstrated by a-ore recent work. 2 Polarisability data are determined experimentally from physical measurements on bulk systems, and therefore reflect a mean molecular property. However, in describing chemical reactivity one has to consider the local, site-specific effect of polarisability on electronic changes induced by reagents. For charge development, stabilisation deriving from a remote atom is less than when the same atom is close to the charged centre.