Probing intramolecular interactions in arylselenides using a property descriptor based approach

Abstract

Although a large volume of experimental evidence is available on the existence of intramolecular nonbonding interactions between chalcogen atoms in main group organometallic compounds, the primary focus has been on the contact distances involving the chalcogen atoms. The important class of intramolecular Se···X (where X is O, S, N) nonbonding interaction in a series of organoselenium compounds is quantified using a new scheme based on a molecular property descriptor. In the present study, we have employed the nucleus-independent chemical shift [NICS(0)] values, as a property descriptor to evaluate the strength of exocyclic nonbonding interactions in a series of aryl selenides. The ab initio MP2 as well as density functional theory methods have been used in conjunction with Dunning’s cc-pVDZ basis set. The quantified values of Se···X nonbonding interactions are compared with other schemes based on thermochemical equations such as homodesmic and ortho−para methods. The changes in NICS(0) values at the aryl ring center are found to be sensitive to the strength of exocyclic Se···X interaction.