Institut de Chimie Moléculaire de Reims, UMR CNRS 7312, Université de Reims, BP 1039, 51687 Reims, France.
Dalton Trans. 2013 Aug 14;42(30):10997-1004. doi: 10.1039/c3dt51158h. Epub 2013 Jun 24.
Mixtures of 2,4- and 2,5-disubstituted zirconacyclopentadienes were obtained by the reductive dimerisation of terminal alkynes using the Cp2ZrCl2/lanthanum system. Reactions of dihalophosphines with these mixtures afforded selectively the corresponding 2,4-disubstituted phospholes and 1,4-disubstituted butadienes. A new series of phospholes was characterized by multi-nuclear NMR spectroscopy and X-ray analysis. A possible explanation for the observed selectivity was obtained from X-ray studies and DFT analysis of the intermediate zirconacyclopentadienes.
使用 Cp2ZrCl2/镧体系还原二聚末端炔烃，可以得到 2,4-和 2,5-二取代的二茂锆混合物。二卤代膦与这些混合物反应，可以选择性地得到相应的 2,4-二取代的磷杂环戊二烯和 1,4-二取代的丁二烯。通过多核 NMR 光谱和 X 射线分析对一系列新的磷杂环戊二烯进行了表征。从 X 射线研究和中间锆茂环戊二烯的 DFT 分析中得到了观察到的选择性的可能解释。
