Modeling intrinsic basicities and acidities

Abstract

AbstractWe illustrate the potential of ab initio and density functional theory (DFT) methods to model and gain some understanding of the intrinsic reactivity of molecules. We show how the use of high‐level ab initio or DFT calculations permit to rationalize (a) basicity and acidity trends along a series of homologous compounds, namely thiocarbonyl and selenocarbonyl derivatives, α,β‐unsaturated amines, phosphines and arsines, and α,β‐unsaturated alkanes, silanes, germanes and stannanes, (b) the role of intramolecular hydrogen bonds in intrinsic acidities and basicities, (c) the incidence of induced proton transfer process effects on the intrinsic basicity of compounds stabilized by intramolecular hydrogen bonds, (d) hybridization effects on intrinsic basicities, (e) the role of non‐classical structures in intrinsic basicities and (f) the observation of bond cleavage associated with gas‐phase protonation and the influence of these dissociative proton attachment mechanisms on the intrinsic basicity of the system. Copyright © 2002 John Wiley & Sons, Ltd.