学术
卤代甲烷核磁共振谱化学位移的QSSR研究
戴益民[1] 邓小清[2] 杨道武[1] 周宏明[3]
[1]长沙理工大学化学与环境工程学院,湖南长沙410076 [2]长沙理工大学物理与电子科学学院,湖南长沙410076 [3]中南大学材料科学与工程学院,湖南长沙410083
摘 要:
利用描述电子效应的诱导效应指数（∑I）、原子的平衡电负性（XE）和反映核外电子云变形程度的总电子数（∑e）、各取代基到中心原子的化学键键长总和（∑d）以及各取代基电负性的和差值（△X）等参数对45个卤代甲烷化合物中的碳原子结构进行表征，并与其^13C NMR谱化学位移建立了优良的定量结构-波谱关系模型：δ=-7403．8022～47．1765∑I＋4290．0270XE-3．3067△X-163．4672∑d-4．5153∑e＋22．9851∑e／∑d＋15．2597∑e／XE-890．2521∑d／XE．所建多元线性回归方程复相关系数R^2及留一法（leave-one-out，LOO）交互验证（cross validation，CV）的复相关系数R^2CV分别为0．9951和0．9950．结果表明所建模型不仅能比现有文献更好地揭示卤代甲烷^13C NMR谱化学位移与其分子结构信息之间的关系，同时也提供一种计算卤代甲烷^13C NMR谱化学位移的新方法．[著者文摘]
文章出处:
《波谱学杂志》-2008年25卷1期 -110-116页
分 类 号:
文献标识码:
A
文章编号:
1000-4556（2008）01-0110-07
A Quantitative Structure-Spectrum Relationship Study of ^13C NMR Chemical Shifts of Halogenated Methane
DAI Yi-min , DENG Xiao-qing , YANG Dao-wu , ZHOU Hong-ming （1. School of Chemical and Environmental Engineering, Changsha University of Science and Technology, Changsha 410076 China; 2. School of Physics and Electronic Science, Changsha University of Science and Technology, Changsha 410076 China;3. School of Material Science and Engineering, Central South University, Changsha 410083, China）
Abstract:
Molecular structural parameters including inductive effect index（∑I）, equilibrium electronegativity of atom （XE）, total electron of atom nuclear external（∑e）, total bond length of substituents to center atom（∑d） and electronegativity margin for all substituents （△X） were used model the ^13C chemical shift of 45 halogenated methane. It was found that the quantitative structure-spectrum relationship model can be expressed as follows： δc =- 7403. 8022 -47. 1765 ∑I＋4290. 0270XE- 3. 3067△X- 163. 4672∑d- 4. 5153 ∑e＋22. 9851 ∑e/∑d＋15. 2597 ∑e/XE- 890. 2521 ∑d/XE. The square of the correlation coefficients of the proposed model in multiple linear regression and cross validation（CV） using leave-one-out （LOO） were 0.9951 and 0.9950, respectively. These results suggested that the model proposed provide a good quantitative structure-spectrum relationship between ^13C NMR chemical shift of halogenated methane and its molecular structural parameters, and could be used to calculate ^13C NMR chemical shift of halogenated methane with known structure.[著者文摘]
Key words:
halogenated methane, chemical shift, molecular structural parameter, quantitative structure-spectrum relationship
基金资助:
湖南省自然科学基金资助项目（05JJ30198）.
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