Visible‐Light Controlled Divergent Catalysis Using a Bench‐Stable Cobalt(I) Hydride Complex

While the use of visible light in conjunction with transition metal catalysis offers powerful opportunities to switch between on/‐off states of catalytic activity, the next frontier would be the ability to switch the actual function of the catalyst and resulting products. Here we report such an example of multi‐dimensional catalysis. Featuring an easily prepared, bench‐stable cobalt(I) hydride complex in conjunction with pinacolborane, we can switch the reaction outcome between two widely employed transformations, olefin migration and hydroboration, with visible light as the trigger. Night and day: A rare example of switching product outcome depending on light‐dark is reported. Using a cobalt(I) hydride complex, hydroborated products are obtained under visible‐light irradiation whereas, in contrast, alkene isomerisation occurs in the dark. This dual‐function catalysis results from alteration of the coordination sphere surrounding the metal centre.