The through‐space transmission of ⁷⁷Se — ⁷⁷Se coupling constants

Abstract

Abstract The IPPP‐INDO method is applied to study different interactions as well as transmission mechanisms of 77 Se — 77 Se coupling constants in cis ‐ and trans ‐1,2‐bis(methylseleno)ethene. Preferential conformations were determined using a modified version of the PCILO‐CNDO method. The preferential conformation of the cis compound is such that nonbonding electron pairs of both Se atoms overlap to some extent. In this conformation a large and positive through‐space transmission of the Fermi contact term of the 77 Se — 77 Se coupling takes place, which strongly depends on the Se — Se distances. The similarity between this coupling and others involving different nuclei is discussed. The total calculated coupling is in fair agreement with experimental values for similar compounds. The 77 Se — 77 Se coupling in the trans‐compound is largely dominated by the orbital interaction, which is mainly transmitted through the vinyl π‐electron system.