Density-functional computation of 93Nb NMR chemical shifts

被引：13

作者：

Buehl, Michael ^{[1
]}

Wrackmeyer, Bernd ^{[2
]}

机构：

[1] Univ St Andrews, Sch Chem, St Andrews KY16 9ST, Fife, Scotland

[2] Univ Bayreuth, D-95440 Bayreuth, Germany

来源：

MAGNETIC RESONANCE IN CHEMISTRY | 2010年 / 48卷

关键词：

NMR; Nb-93; density-functional calculations; chemical-shift computations; electric field gradient; TRANSITION-METAL-COMPLEXES; MOLECULAR-STRUCTURE; CRYSTAL-STRUCTURES; ROOM-TEMPERATURE; X-RAY; CORRELATION-ENERGY; NIOBIUM; TANTALUM; HEXACHLORONIOBATE(V); HEXAFLUORONIOBATE;

D O I：

10.1002/mrc.2624

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Nb-93 chemical shifts of [NbX6](-) (X = Cl, F, CO), [NbXCl4](-) (X = O, S), Nb-2(OMe)(10), Cp*Nb-2(kappa(2)-BH4), (Cp*Nb)(2)(mu-B2H6)(2), CpNb(CO)(4), and Cp2NbH3 are computed at the GIAO (gauge-including atomic orbitals)-, BPW91- and B3LYP-, and CSGT (continuous set of gauge transformations)-CAM-B3LYP, -omega B97, and -omega B97X levels, using BP86-optimized or experimental (X-ray) geometries. Experimental chemical shifts are best reproduced at the GIAO-BPW91 level when delta(Nb-93) values of inorganic complexes are referenced directly relative to (NbC16)- and those of organometallic species are first calculated relative to [Nb(CO)(6)](-). An inadvertent error in the reported delta(Nb-93) values of cyclopentadiene borane complexes (H. Brunner et al., J. Organomet. Chem. 1992, 436, 313) is corrected. Trends in the observed Nb-93 NMR linewidths for anionic niobates [Nb(CO)(5)](3-), [Nb(CO)(5)H](2-), and [Nb(CO)(5)(NH3)](-) are rationalized in terms of computed electric field gradients at the metal. Copyright (C) 2010 John Wiley & Sons, Ltd.

引用

页码：S61 / S68

页数：8

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