Abstract
[{Ir(μ-OMe)(diolef)}2]/phosphane systems are active catalysts for hydrogen transfer reactions following a hydrido route mechanism, according to DFT studies. [Display omitted]
•Diolefin iridium complexes are catalysts for acetophenone reduction.•The influence of P- and N-donor ligands in the catalytic activity has been studied.•DFT theoretical methods showed the transfer mechanism follows a hydrido route.
Methoxo-bridged diiridium complexes of the type [{Ir(μ-OMe)(diolefin)}2] (diolefin=1,5-cyclooctadiene, tetrafluorobenzobarrelene), in the presence on P- or N-donor ligands, are active catalyst precursors in the catalytic hydrogen transfer of iPrOH to acetophenone. Both the nature of the diolefin and that of additional P- and N-donor ligands have a marked effect in the catalytic outcome of the reactions. DFT theoretical studies have been carried out on the binary catalytic systems composed of the iridium complexes and mono phosphanes (Ir/P=1/1), which indicated that the operative mechanism in these transformations follows the classic “hydrido” route.