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A highly tunable phosphine–imine ligand family is introduced. Following metallation with ruthenium, deprotonation of the ligand affords a phosphine–enamido species. Complexes with the ligand in both the imine and enamido forms are active toward acceptorless dehydrogenation reactions.

Graphical abstract: Phosphine–imine and –enamido ligands for acceptorless dehydrogenation catalysis

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