Density-functional computation of 53Cr NMR chemical shifts

被引:15
作者
Buehl, Michael [1 ]
机构
[1] Max Planck Inst Kohlenforsch, D-45470 Mulheim, Germany
关键词
NMR; Cr-53; density-functional calculations; chemical-shift computations; electric field gradients;
D O I
10.1002/mrc.1807
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Cr-53 chemical shifts of CrO42-, Cr2O72-, CrO3X-, CrO2X2(X = F, Cl), and Cr(CO)(5)L (L = CO, PF3, CHNH2, CMeNMe2) are computed, using geometries optimized with the gradient-corrected BP86 density functional, at the gauge-including atomic orbitals (GIAO)-, BPW91-, and B3LYP levels. For this set of compounds, substituent effects on delta(Cr-53) are better described with the pure BPW91 functional than with B3LYP, in contrast to most other transition-metal chemical shifts studied so far. For selected cases, Cr-53 NMR line widths can be rationalized in terms of electric field gradients (EFGs) computed with the BPW91 functional, but in general other factors such as molecular correlation times appear to be dominating. Cr-53 chemical shifts and EFGs are predicted for CrO3, Cr(C6H6)(2), Cr(C6H6)CO3, and, with reduced reliability, for Cr-2(mu(2)-O2CH)(4). Copyright (c) 2006 John Wiley & Sons, Ltd.
引用
收藏
页码:661 / 668
页数:8
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