An effective visible-light-promoted iridium(III)-catalyzed hydrogen production from N-heterocycles is described. A single iridium complex constitutes the photocatalytic system playing a dual task, harvesting visible-light and facilitating C–H cleavage and H 2 formation at room temperature and without additives. The presence of a chelating C–N ligand combining a mesoionic carbene ligand along with an amido functionality in the Ir III complex is essential to attain the photocatalytic transformation. Furthermore, the Ir III complex is also an efficient catalyst for the thermal reverse process under mild conditions, positioning itself as a proficient candidate for liquid organic hydrogen carrier technologies (LOHCs). Mechanistic studies support a light-induced formation of H 2 from the Ir–H intermediate as the operating mode of the iridium complex.

The activation of C−H bonds in a selective manner still constitutes a major challenge from a synthetic point of view; thus, it remains an active area of fundamental and applied research. Herein, we introduce ion mobility spectrometry mass spectrometry-based (IM-MS) approaches to uncover site-selective C−H bond activation in a series of metal complexes of general formula [(NHC)LMCl] + (NHC = N-heterocyclic carbene; L = pentamethylcyclopentadiene (Cp*) or p-cymene; M = Pd, Ru, and Ir). The C−H bond activation at the N-bound groups of the NHC ligand is promoted upon collision induced dissociation (CID). The identification of the resulting [(NHC-H)LM] + isomers relies on the distinctive topology that such cyclometalated isomers adopt upon site-selective C−H bond activation. Such topological differences can be reliably evidenced as different mobility peaks in their respective CID-IM mass spectra. Alternative isomers are also identified via dehydrogenation at the Cp*/p-cymene (L) ligands to afford [(NHC)(L-H)M] + . The fragmentation of the ion mobility-resolved peaks is also investigated by CID-IM-CID. It enables the assignment of mobility peaks to the specific isomers formed from C(sp 2 )−H or C(sp 3 )−H bond activation and distinguishes them from the Cp*/p-cymene (L) dehydrogenation isomers. The conformational change of the NHC ligands upon C−H bond activation, concomitant with cyclometalation, is also discussed on the basis of the estimated collision cross section (CCS). A unique conformation change of the pyrene-tagged NHC members is identified that involves the reorientation of the NHC ring accompanied by a folding of the pyrene moiety.

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