Modeling continuous changes in substituent electronegativity and chemical hardness using fictitious nuclear potentials

摘要: Electronegativity and chemical hardness are important conceptual tools in organic organometallic chemistry. Computational chemistry can aid understanding of these concepts by simulating fictitious substituents with smoothly varying electronegativity hardness. This work shows that Gaussian smearing an atom’s nuclear charge distribution enables variation its hardness, without changing the total molecule charge. Tunable covalent, Lewis acid, base give chemically reasonable results several canonical reactions. These include hard–soft acid–base effects on thiocyanate enolate isomerization, ligand trans influences stability complexes thermodynamics reductive elimination, substituent proton affinities benzene derivatives. The illustrate utility motivate their use as interpretive tools.