Abstract
Nuclear couplings for the Se-Se bonds, 1 J(Se, Se), are analyzed on the basis of the molecular orbital (MO) theory. The values are calculated by employing the triple ζ basis sets of the Slater type at the DFT level. 1 J(Se, Se) are calculated modeled by MeSeSeMe (1a), which shows the typical torsional angular dependence on ϕ(CMeSeSeCMe). The dependence explains well the observed 1 J obsd (Se, Se) of small values (≤ 64 Hz) for RSeSeR′ (1) (simple derivatives of 1a) and large values (330–380 Hz) observed for 4-substituted naphto[1,8-c, d]-1,2-diselenoles (2) which correspond to symperiplanar diselenides. 1 J (Se, Se: 2) becomes larger as the electron density on Se increases. The paramagnetic spin-orbit terms contribute predominantly. The contributions are evaluated separately from each MO (ψ i) and each ψ i → ψ a transition, where ψ i and ψ a are occupied and unoccupied MO's, respectively. The separate evaluation enables us to recognize and visualize the origin and the mechanism of the couplings.
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.