Theoretical Study of Metal NMR Chemical Shifts. Selenium Compounds

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Abstract
The 77Se chemical shifts of nine selenium compounds, SeRR′ (R, R′ = H, Me, Et, Ph, SiH3, GeH3), are theoretically investigated by ab initio Hartree–Fock/finite perturbation method. The calculated values agree well with the experimental values. The Se chemical shift is dominated by the Se valence 4p AO contribution to the paramagnetic term, and shows a parallelism with the 4p-hole population and the net charge of the central Se atom. The Se chemical shift moves downfield as an increase of the hole in the 4p orbitals, and therefore, as an increase in the electron-withdrawing ability of the ligands attached to the selenium atom.