Mapping the Ultrafast Mechanistic Pathways of Co Photocatalysts in Pure Water through Time‐Resolved X‐ray Spectroscopy
Abstract Nanosecond time‐resolved X‐ray (tr‐XAS) and optical transient absorption spectroscopy (OTA) are applied to study 3 multimolecular photocatalytic systems with [Ru(bpy) 3 ] 2+ photoabsorber, ascorbic acid electron donor and Co catalysts with methylene ( 1 ), hydroxomethylene ( 2 ) and methyl ( 3 ) amine substituents in pure water. OTA and tr‐XAS of 1 and 2 show that the favored catalytic pathway involves reductive quenching of the excited photosensitizer and electron transfer to the catalyst to form a Co II square pyramidal intermediate with a bonded aqua molecule followed by a Co I square planar derivative that decays within ≈8 μs. By contrast, a Co I square pyramidal intermediate with a longer decay lifetime of ≈35 μs is formed from an analogous Co II geometry for 3 in H 2 O. These results highlight the protonation of Co I to form the elusive hydride species to be the rate limiting step and show that the catalytic rate can be enhanced through hydrogen containing pendant amines that act as H−H bond formation proton relays.