A dependence of reactivity or stability on the spatial alignment of donor and acceptor orbitals. Antiperiplanar lone-pair donation into a breaking bond can accelerate a suitable cleavage.

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The stereoelectronic effect refers to the influence of molecular geometry on electronic interactions and reactivity, particularly in the context of chemical bonding and reaction mechanisms. It describes how the spatial arrangement of atoms and the orientation of orbitals can affect the electronic properties of a molecule and, consequently, its reactivity. In essence, the stereoelectronic effect highlights the relationship between the arrangement of bonds in three-dimensional space and the electron distribution in molecular orbitals.