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Published on: February 7, 2019
Reactivity differences between 2,4- and 2,5-disubstituted zirconacyclopentadienes: a highly selective and general
Guillaume Bousrez1, Florian Jaroschik, Agathe Martinez
1Institut de Chimie Moléculaire de Reims, UMR CNRS 7312, Université de Reims, BP 1039, 51687 Reims, France.
Abstract:
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.
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