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The through‐space transmission of 77 Se — 77 Se coupling constants
Author(s) -
Contreras R. H.,
Gavarini H. O.,
Natiello M. A.
Publication year - 1987
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.540080306
Subject(s) - cndo/2 , coupling constant , chemistry , coupling (piping) , computational chemistry , space (punctuation) , molecular orbital , crystallography , fermi contact interaction , similarity (geometry) , electron , transmission (telecommunications) , chemical physics , molecular physics , stereochemistry , physics , molecule , materials science , quantum mechanics , organic chemistry , artificial intelligence , computer science , electrical engineering , image (mathematics) , engineering , linguistics , philosophy , metallurgy
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.