Dodziuk Helena, Jaszuński Michał, Schilf Wojciech
Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland.
Magn Reson Chem. 2005 Aug;43(8):639-46. doi: 10.1002/mrc.1598.
The NMR parameters characterizing the spectra of trans- and cis-decalins were determined from theoretical calculations and experimental spectra. The calculated values of the shielding constants are in good agreement with the measured chemical shifts, with a small but noticeable difference in accuracy for the bridgehead atoms. Of all the spin-spin coupling constants, only most of (1)J(C,C) and (1)J(C,H) values could be extracted from the spectra, and the corresponding computed values are in good agreement with experiment. It appears that the applied density functional theory (DFT) approach overestimates slightly the J(C,C) coupling and underestimates the differences between one-bond (1)J(C,H) coupling constants. For all these constants [J(C,C), J(C,H) and J(H,H)] through one to three bonds, which could not be obtained experimentally, the predicted values are in good agreement with the general rules relating spin-spin coupling to the number and spatial arrangement of the intervening bonds.
通过理论计算和实验光谱确定了表征反式和顺式十氢化萘光谱的核磁共振参数。屏蔽常数的计算值与测量的化学位移吻合良好，桥头原子的精度存在微小但明显的差异。在所有自旋 - 自旋耦合常数中，只有大部分(1)J(C,C)和(1)J(C,H)值可从光谱中提取，相应的计算值与实验结果吻合良好。似乎所应用的密度泛函理论(DFT)方法略微高估了J(C,C)耦合，并低估了一键(1)J(C,H)耦合常数之间的差异。对于所有这些通过一到三个键的常数[J(C,C)、J(C,H)和J(H,H)]，虽然无法通过实验获得，但预测值与将自旋 - 自旋耦合与中间键的数量和空间排列相关的一般规则吻合良好。
