¹³C and ¹⁵N NMR spectra of high-energy polyazidocyanopyridines

详细信息    查看全文

• 作者：Sergei V. Chapyshev ; Alexander V. Chernyak and Evgeny N. Ushakov
• 刊名：Magnetic Resonance in Chemistry
• 出版年：2017
• 出版时间：February 2017
• 年：2017
• 卷：55
• 期：2
• 页码：99-105
• 全文大小：669K
• ISSN：1097-458Xa

文摘

¹³C and ¹⁵N NMR spectra of high-energy 2,4,6-triazidopyridine-3,5-dicarbonitrile, 2,3,5,6-tetraazidopyridine-4-carbonitrile and 3,4,5,6-tetraazidopyridine-2-carbonitrile are reported. The assignment of signals in the spectra was performed on the basis of density functional theory calculations. The molecular geometries were optimized using the M06-2X functional with the 6-311+G(d,p) basis set. The magnetic shielding tensors were calculated by the gauge-independent atomic orbital method with the Tao–Perdew–Staroverov–Scuseria hybrid functional known as TPSSh. In all the calculations, a polarizable continuum model was used to simulate solvent effects. This approach provided accurate predictions of the ¹³C and ¹⁵N chemical shifts for all the three compounds despite complications arising due to non-coplanar arrangement of the azido groups in the molecules. It was found that the ¹⁵N chemical shifts of the N_α atoms in the azido groups of 2,4,6-triazidopyridines correlate with the ¹³C chemical shifts of the carbon atoms attached to these azido groups. Copyright