离子性指数、立体效应参数与膦类化合物^(31)P NMR δ_P的关系  

Calculating ^(31)P Chemical Shifts of Phosphines Based on the Ionicity Index and Stereoscopic Effect Index of the Compounds

作　　者：仝建波[1] 张生万[1] 赵毅[1] 

机构地区：[1]山西大学化学化工学院,山西太原030006

出　　处：《波谱学杂志》2006年第2期261-269,共9页Chinese Journal of Magnetic Resonance

基　　金：山西省自然科学基金项目(20041013);山西省工业攻关基金项目(2006031204)

摘　　要：利用离子性指数(INI)和立体效应参数(α、β、γ)对100个膦化合物中磷原子进行结构表征,并与其核磁共振磷谱(31P NMR)建立了优良的定量构谱相关(QSSR)模型:δP=-163.695 3-1.003 1INI+34.632 7α+13.892 9β-3.331 7γ.建模的计算值、留一法(Leave-One-Out,LOO)交互校验(Cross-Validation,CV)预测值的复相关系数(R)分别为0.976 5和0.973 9.所建模型不仅在一定程度上阐明了膦类化合物31P NMR谱化学位移与其分子结构信息之间的关系,同时也提供了一种从理论上计算膦类化合物31P NMR谱化学位移的新方法,并对深入了解膦类化合物结构与性能的关系及解析、预测其31P NMR谱提供了一定的理论依据.A model was proposed for calculating ^31p chemical shifts of the phosphorus atoms in phosphine and its derivatives from the ionicity indices （INI） and the stereoscopic effect parameters （α, β, γ） of the compounds： δp = -163. 695 3 - 1. 003 1INI ＋ 34. 632 7α＋13. 892 9β-3. 331 7γ. Correlation coefficients of the proposed model and leave-one-out cross-validation were 0. 976 5 and 0. 973 9, respectively. Tfiis model not only provides a new method to calculate ^31p chemical shifts of phosphines, but also establishes the relationship between the ^31p chemical shifts of phosphines and their molecular structures. In addition, it can be used to predict the 31p chemical shifts of phosphine derivatives.

关 键 词：^31P NMR 膦类化合物 离子性指数 立体效应参数 

分 类 号：O641[理学—物理化学]