Molecular orbital studies in Mo-95 NMR shielding for [MoOnS4-n](2-) anions: Relations between chemical shift and molybdenum orbital electron populations

被引:6
作者
Teruel, H [1 ]
Sierralta, A [1 ]
机构
[1] INST VENEZOLANO INVEST CIENT, CTR QUIM, CARACAS 1010A, VENEZUELA
关键词
D O I
10.1016/0277-5387(95)00476-9
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The Mo-95 NMR chemical shifts of [MoO4-nSn](2-) (n = 0-4) have been analysed theoretically by semi-empirical, CNDO and ab initio molecular orbital methods. The calculated values of molybdenum chemical shifts by correlating molybdenum p- and d-orbital electron populations or the molybdenum total electron charge agreed well with the available experimental data on \Delta delta\ approximate to 20 ppm compared with the previously reported \Delta delta\ approximate to 140-300 ppm using similar calculation methods. The Mo chemical shift reflects the change in the valence 4d- and 5p-orbitals of molybdenum, but it is mainly determined by the p-orbital electron population by a factor beyond 10. This unequal contribution to the molybdenum shielding reflects the relevance of p-orbitals in pi-back-bonding for these compounds.
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页码:2215 / 2221
页数:7
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