Abstract
Abstract Values of the σ* constants have been defined for some m- and p-substituted phenyl groups from the 29Si–H coupling constants for a series of m- and p-substituted phenylsilanes, phenylmethylsilanes, and phenyldimethylsilanes. The σ* constants for the groups, XC6H4, were found to be directly related to the Hammett σ constants for the ring substituents, X. From this correlation the σ* constants for a number of other substituted phenyl groups have also been calculated. Examples have been presented in which a simple relationship holds between the Taft polar substituent constants including the newly derived σ* constants and molecular properties for a series of compounds covering both aliphatic and aromatic substances. Correlations of reactivities with the extended σ* values have been illustrated and the implications of the results are discussed.
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