How (77)Se NMR chemical shifts originate from pre-alpha, alpha, beta, and gamma effects: interpretation based on molecular orbital theory.

Plain rules founded in a theoretical background are presented that can be used to determine the structure of selenium compounds on the basis of delta(Se) data and to predict delta(Se) data from a given structure with satisfactory accuracy. As a first step to establish such rules, the origin of delta(Se) is elucidated on the basis of MO theory. The Se(2-) ion was chosen as the standard for the analysis. The concept of the pre-alpha effect is proposed, which is defined as the downfield shift due to protonation of a lone-pair orbital of Se. The pre-alpha effect of two protons in H(2)Se is explained by the generation of double sigma(Se--H) and sigma*(Se--H) through protonation of the spherical Se(2-) ion. The orbitals, together with n(p)(Se), result in effective transitions for the pre-alpha effect. The alpha effect is the downfield shift caused by the replacement of Se--H by Se--Me. The extension of HOMO-2 [4p(y)(Se)], HOMO-1 [4p(x)(Se)], and HOMO [4p(z)(Se)] over the whole Me(2)Se molecule is mainly responsible for the alpha effect. The beta effect originates not from the occupied-to-unoccupied (psi(i)-->psi(a)) transitions but from the occupied-to-occupied (psi(i)-->psi(j)) transitions. Although psi(i)-->psi(j) transitions contribute to upfield shifts in Me(2)Se, the magnitudes become smaller as the methyl protons are substituted by Me groups one after another. The gamma effect of upfield shifts is also analyzed, although complex. The effect of p(Se)-pi(C==C) conjugation is analyzed in relation to the orientational effect. Contributions from each MO (psi(i)) and each psi(i)-->psi(a) transition are evaluated separately, by using a utility program derived from the Gaussian 03 program suite (NMRANAL-NH03G). The treatment enables us to visualize and understand the origin of (77)Se NMR chemical shifts.