Origin of 77Se NMR chemical shifts revealed for pre-α, α, β, and γ effects

被引：2
|
作者：
Hayashi, Satoko [1 ]
Nakanishi, Waro [1 ]
机构：
[1] Wakayama Univ, Fac Syst Engn, Dept Chem, Wakayama 6408510, Japan
来源：
PHOSPHORUS SULFUR AND SILICON AND THE RELATED ELEMENTS | 2008年 / 183卷 / 04期
关键词：
Ab initio calculations; alpha beta gamma effects; GIAO; origin of Se-77 NMR chemical shifts; paramagnetic shielding constants; pre-alpha effect;
D O I：
10.1080/10426500801901129
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
The origin of delta(Se) is revealed based on the MO theory. The pre-alpha effect in H2Se, defined in the text, is the generation of double (Se-H) and sigma*(Se-H) through the protonation to spherical Se2-. The extension of HOMO-n (n = 0, 1, and 2) over the whole molecule of Me2Se is mainly responsible for the alpha effect. The beta effect originates not from the occupied-to-unoccupied transitions but from the occupied-to-occupied transitions. The gamma effect of the upfield shifts is the results of the subtle balance between two types of transitions. Contributions from each MO (psi(i)) and each psi(i) --> psi(a) transition are evaluated separately, using a utility program (NMRANAL-NH03G).
引用
收藏
页码：1067 / 1071
页数：5
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