Vicinal tungsten-tungsten coupling constants in polyoxotungstates: DFT calculations challenge an empirical rule

被引：30

作者：

Bagno, A

Bonchio, M

机构：

[1] Univ Padua, Dept Chem, I-35131 Padua, Italy

[2] CNR, Inst Membrane Technol, Padova Sect, I-35131 Padua, Italy

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2005年 / 44卷 / 13期

关键词：

density functional calculations; NMR spectroscopy polyoxometalates; spin-spin coupling; tungsten;

D O I：

10.1002/anie.200462292

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

(Chemical Equation Presented) Smaller than expected: The empirical rule that edge and corner junctions give rise to small and large vicinal NMR tungsten-tungsten coupling constants, respectively, in polyoxometalates has led to the assumption that the W-O-W angle is the sole factor involved. Why then is the corner 2JWW coupling in γ-[SiW 10O36]8- (see picture) so small? Relativistic DFT calculations show why this is indeed expected. © 2005 Wiley-VCH Verlag GmbH & Co. KGaA.

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页码：2023 / 2026

页数：4

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