Solid-state NMR fermi contact and dipolar shifts in organometallic complexes and metalloporphyrins.
Solid-state NMR fermi contact and dipolar shifts in organometallic complexes and metalloporphyrins.
复制标题
有机金属配合物和金属卟啉中的固态核磁共振费米接触和偶极位移。
DOI：
10.1021/ja043461j
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发表时间：
2005
影响因子：
15
通讯作者：
Oldfield,Eric
中科院分区：
文献类型：
--
作者：
Zhang,Yong;Sun,Haihong;Oldfield,Eric
利用密度泛函理论方法研究了顺磁性有机金属配合物和金属卟啉的固态“魔角”自旋（MAS）核磁共振和单晶核磁共振/ENDOR谱。固态MAS NMR化学位移（包括抗磁性和超细贡献）预测斜率为1.007,anR2= 0.967，对应于整个442 ppm范围内的28 ppm（或6.3%）误差。单晶ENDOR超精细值，包括各向同性费米接触和偶极耦合，预测斜率为1.009,anR2= 0.998，对应于整个78.37 MHz范围内的0.93 MHz（或1.2%）误差。此外，预测单晶核磁共振位移（包括两个超精细项）的anR2= 0.961。计算固态MAS NMR和单晶NMR/ENDOR数据的能力应该有助于这些技术在研究顺磁性金属配合物中的使用，并且应该特别用于研究顺磁性金属蛋白，其中结构不太准确。
We have used density functional theory methods to investigate the solid-state “magic-angle” spinning (MAS) NMR and single-crystal NMR/ENDOR spectra of paramagnetic organometallic complexes and metalloporphyrins. The solid-state MAS NMR chemical shifts (including both diamagnetic and hyperfine contributions) are predicted with a slope of 1.007 and anR2= 0.967, corresponding to a 28 ppm (or 6.3%) error over the entire 442 ppm range. Single-crystal ENDOR hyperfine values, including both isotropic Fermi contact and dipolar couplings, are predicted with a slope of 1.009 and anR2= 0.998, corresponding to a 0.93 MHz (or 1.2%) error over the entire 78.37 MHz range. In addition, single-crystal NMR shifts (including both hyperfine terms) are predicted with anR2= 0.961. The ability to compute solid-state MAS NMR and single-crystal NMR/ENDOR data should facilitate the use of these techniques in investigating paramagnetic metal complexes and should be of particular use in studying paramagnetic metalloproteins, where structures are less accurately known.