Electrocatalytic Transfer Hydrogenation of 1-Octene with [(tBuPCP)Ir(H)(Cl)] and Water

Electrocatalytic hydrogenation of 1-octene as nonactivated model substrate with neutral water as H-donor is reported, using [(tBuPCP)Ir(H)(Cl)] (1) as the catalyst, to form octane with high faradaic efficiency (FE) of 96% and a kobs of 87 s–1. Cyclic voltammetry with 1 revealed that two subsequent reductions trigger the elimination of Cl– and afford the highly reactive anionic Ir(I) hydride complex [(tBuPCP)Ir(H)]– (2), a previously merely proposed intermediate for which we now report first experimental data by mass spectrometry. In absence of alkene, the stoichiometric electrolysis of 1 in THF with water selectively affords the Ir(III) dihydride complex [(tBuPCP)Ir(H)2] (3) in 88% FE from the reaction of 2 with H2O. Complex 3 then hydrogenates the alkene in classical fashion. The presented electro-hydrogenation works with extremely high FE, because the iridium hydrides are water stable, which prevents H2 formation. Even in strongly alkaline conditions (Bu4NOH added), the electro-hydrogenation of 1-octene with 1 also proceeds cleanly (FE = 89%), suggesting a highly robust process that may rely on H2O activation, reminiscent to transfer hydrogenation pathways, instead of classical H+ reduction