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Reversible cyclometalation is demonstrated as a strategy for the activation of small protic molecules, with a proof-of-principle catalytic application in the dehydrogenation of formic acid in the absence of an exogenous base. The well-defined RhI complex Rh(CO)(L) 1, bearing the reactive cyclometalated PN(C) ligand L (LH = PNCH = 2-di(tert-butylphosphinomethyl)-6-phenylpyridine), undergoes protonolysis of the Rh-CPh bond with weak protic reagents, such as thiols and trifluoromethanesulfonamide. This system also displays bifunctional metal-ligand protonolysis reactivity with formic acid and subsequent decarboxylation of the formate complex. Density functional theory (DFT) calculations show that H2 evolution from putative Rh(CO)(H)(LH) complex A is very facile, proposedly encompassing formal C-H oxidative addition at Rh to give Cvia agostic intermediate B and subsequent reductive elimination of H2. Complex 1 is a catalytically competent species for base-free formic acid dehydrogenation, with the intermediacy of formate complex 4. DFT calculations reveal accessible barriers for involvement of a flanking phenyl group for both initial activation of formic acid and release of H2, supporting a cooperative pathway. Reversible C-H activation is thus a viable mechanism for metal-ligand bifunctional catalysis

Reversible cyclometalation at RhI as a motif for metal–ligand bifunctional bond activation and base-free formic acid dehydrogenation

Reversible cyclometalation at Rh^I as a motif for metal–ligand bifunctional bond activation and base-free formic acid dehydrogenation