A catalytic system based on an iridium–PNP complex was developed for the aqueous‐phase reforming of methanol. Investigations revealed higher activity at low base concentrations and higher stability at high base concentrations as an opposing trend relative to that of known Ru and Fe PNP‐pincer‐containing systems for methanol dehydrogenation. During mechanistic investigations it was possible to identify a CO containing derivate of the deactivation species.

The ruthenium complex [RuH (PPh ) ] is a competent catalyst for the selective dehydrogenation of formic acid (FA) at low temperature. It tolerates water and shows excellent performance (TOF up to 36 000 h at 60 °C). Remarkably, no basic additives are necessary to obtain such high activity and the defined complex is stable for up to 120 days, making this system one of the most effective formic acid dehydrogenation catalysts known to date.