Reactivity differences between 2,4- and 2,5-disubstituted zirconacyclopentadienes: a highly selective and general approach to 2,4-disubstituted phospholes. - École polytechnique
Article Dans Une Revue Dalton Transactions Année : 2013

Reactivity differences between 2,4- and 2,5-disubstituted zirconacyclopentadienes: a highly selective and general approach to 2,4-disubstituted phospholes.

Résumé

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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Dates et versions

hal-00839784 , version 1 (01-07-2013)

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Guillaume Bousrez, Florian Jaroschik, Agathe Martinez, Dominique Harakat, Emmanuel Nicolas, et al.. Reactivity differences between 2,4- and 2,5-disubstituted zirconacyclopentadienes: a highly selective and general approach to 2,4-disubstituted phospholes.. Dalton Transactions, 2013, epub ahead of print. ⟨10.1039/c3dt51158h⟩. ⟨hal-00839784⟩
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