1966 Volume 39 Issue 10 Pages 2094-2101
The effects of ring substituents on the stability of silver ion complexes of benzene and styrene are discussed in terms of the delocalization energies as calculated by the simple LCAO MO method. It is demonstrated that the delocalization energy responsible for the formation of the σ -type molecular bond can predict the relative stabilities of the complexes; the calculated energies are linearly correlated with Hammett’s sigma values. The π-type molecular bond energy arising from the delocalization of silver d-electrons decreases linearly with the increase in the σ-type bond energy. In cases where the two energies are comparable in magnitude, the substituent effects may well be controlled by the entropy term, as has previously been demonstrated experimentally. This apparent paradox encountered in the interpretation of substituent effects may best be reconciled by assuming that the behavior of the silver 4d-orbital in complexation is more closely associated with the entropy change than that of the 5s-orbital of the same atom.
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