Koch Rainer, Bruhn Torsten
Institut für Reine und Angewandte Chemie, Carl von Ossietzky Universität Oldenburg, P.O. Box 2503, 26111, Oldenburg, Germany.
J Mol Model. 2006 Jul;12(5):723-9. doi: 10.1007/s00894-005-0081-z. Epub 2006 Mar 29.
49Ti chemical shifts for a total of 20 titanium complexes are reported, and several levels of theory are evaluated in order to identify a reliable approach for the calculation of titanium NMR data. The popular B3LYP/6-31G(d)//B3LYP/6-31G(d) proves to give very good agreement with experimental data over a range from 1,400 to -1,300 ppm. The MP2/6-31G(d)//MP2/6-31G(d) level computes even smaller average deviations but fails for TiI(4). This behavior together with its huge demand for computational resources requires careful handling of this theoretical level. In addition, NMR data for five titanium fulvene (or related) complexes are given.
报道了总共20种钛配合物的49Ti化学位移，并评估了几种理论水平，以确定计算钛核磁共振数据的可靠方法。流行的B3LYP/6-31G(d)//B3LYP/6-31G(d)方法在1400至-1300 ppm范围内与实验数据显示出非常好的一致性。MP2/6-31G(d)//MP2/6-31G(d)水平计算出的平均偏差更小，但对TiI(4)不适用。这种行为及其对计算资源的巨大需求需要谨慎处理该理论水平。此外，还给出了五种钛富烯（或相关）配合物的核磁共振数据。
