Standard enthalpies of formation of organometallic compounds of the I–VI and VIII group elements of the Periodic Table: correlation analysis of the influence of substituents

Published results on the standard enthalpies of formation (Δ_fH°) of 22 narrow series of compounds of the I–VI and VIII group elements of the Periodic Table are analyzed. When these compounds are formed from simple substances, an excess charge appears on the reaction center, inducing a dipole in the substituent, which leads to an ion-dipole interaction (polarizability effect). It is shown for the first time that the thermodynamic characteristic Δ_fH° depends not only on classical (inductive, resonance, and steric) effects, but also on the polarizability effect of the substituents. In some series, the polarizability effect demonstrates the dominant influence on Δ_fH°.