Olefin isomerization by iridium pincer catalysts. Experimental evidence for an η3-allyl pathway and an unconventional mechanism predicted by DFT calculations.

The isomerization of olefins by complexes of the pincer-ligated iridium species ((tBu)PCP)Ir ((tBu)PCP = κ(3)-C(6)H(3)-2,6-(CH(2)P(t)Bu(2))(2)) and ((tBu)POCOP)Ir ((tBu)POCOP = κ(3)-C(6)H(3)-2,6-(OP(t)Bu(2))(2)) has been investigated by computational and experimental methods. The corresponding dihydrides, (pincer)IrH(2), are known to hydrogenate olefins via initial Ir-H addition across the double bond. Such an addition is also the initial step in the mechanism most widely proposed for olefin isomerization (the "hydride addition pathway"); however, the results of kinetics experiments and DFT calculations (using both M06 and PBE functionals) indicate that this is not the operative pathway for isomerization in this case. Instead, (pincer)Ir(η(2)-olefin) species undergo isomerization via the formation of (pincer)Ir(η(3)-allyl)(H) intermediates; one example of such a species, ((tBu)POCOP)Ir(η(3)-propenyl)(H), was independently generated, spectroscopically characterized, and observed to convert to ((tBu)POCOP)Ir(η(2)-propene). Surprisingly, the DFT calculations indicate that the conversion of the η(2)-olefin complex to the η(3)-allyl hydride takes place via initial dissociation of the Ir-olefin π-bond to give a σ-complex of the allylic C-H bond; this intermediate then undergoes C-H bond oxidative cleavage to give an iridium η(1)-allyl hydride which "closes" to give the η(3)-allyl hydride. Subsequently, the η(3)-allyl group "opens" in the opposite sense to give a new η(1)-allyl (thus completing what is formally a 1,3 shift of Ir), which undergoes C-H elimination and π-coordination to give a coordinated olefin that has undergone double-bond migration.