Reactivity of TpMe2-Containing Hydride–Iridafurans with Alkenes, Alkynes, and H2

The TpMe2-containing hydride-iridafurans 2a,b (TpMe2 = hydrotris­(3,5-dimethylpyrazolyl)­borate) cleanly reacted with ethylene to give the bicyclic derivatives 6a,b. Formation of the latter complexes is a reversible process, and it is proposed to occur by an electrocyclic ring closure that takes place between C2H4 and the 16e unsaturated intermediates A, resulting from hydride migration to the α carbon of the metallacycle. Similar reactions were observed with a variety of alkynes RCCR (R = H, Ph, CO2Me) and R′CCH (R′= CO2Me, Ph, CMe3), with the regioselectivity observed for the latter substrates depending on the nature of R′. In the case of Me3SiCCH the structure of an unexpected byproduct indicates that an alkyne–vinylidene rearrangement has taken place on the metal coordination sphere during the reaction, and this observation suggests that in the mechanism of all these coupling processes the corresponding π adducts are active intermediates. Finally, complexes 2a,b reacted with H2 to give products derived from the hydrogenation of their alkenyl arms.