硫代磷酸酯类化合物的^(31)P化学位移加和规则

Additivity Rule of ^(31)P Chemical Shifts for Thiophosphates

对近80种自行合成的硫逐及硫赶磷酸酯类化合物进行了31PNMR谱的测定，提出了一个经验方程、一套化学位移参数和立体电子效应参数，比较准确地计算了它们的31P化学位移．其计算值与测定值的平均误差为±0．096，标准偏差为±0．13．同时，就取代基的电负性、键角和立体电子效应等因素对31P化学位移的影响作了理论上的探讨．

31P NMR spectra of about 80 thiiphisphates synthesized in our laboratory weredetermined- An empirical additivity equation, a set of chemical shift parameters and stereo-electronic effect parameters, which were proposed by the authors, can be used for calculatingslP chemical shifts of phosphates and thiophosphates more accurately. The mean error andthe standard deviation between calculated and observed values of 31 P chemical shifts are±0.096 and ±0.13 respectively- Structures of thiophosphates can be predicted by using theadditivity equation- The dependence of the 31P chemical shifts upon electronegativity, bond-angle and stereoelectronic effect was discussed theoretically.