The mechanistic role of η2-vinyl complexes in metal-promoted alkyne oligomerisations. The crystal and molecular structures of [W{η5-C(CF3)C(CF3)C(CO2Me )C(CO2Me)C(CF3)C(CF3)SPri}(η5-C5H5)], [WF {η5-C(CF2)C(CF3)C( CO2Me)C( CO2Me)C(CF3)C(CF3)SPri}(η5-C5H5)], and [W{η4-C(CF3)C(CF3)C(Me)C(Me)SPri}(η2-CF3CCCF3)(η5-C5H5)]

Abstract
Reactions of Alkynes RCCR (R = CF3, CO2Me, or Me) with η2-vinyl complexes [W{η2-C(CF3)C(CF3)SR′}(CF3CCCF3)(η5-C5H5)](R′= Et, Prn, or Pri) give isomeric products [W(CF3C2CF3)2(RC2R)SR′(η5-C5H5)] resulting from insertion of the incomingalkyne into the MC bond of the η2-vinyl and thus illustrate that η2-vinyls can act as intermediates in metal-promoted alkyne oligomerisation reactions.

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