Iron Dihydride Complex Stabilized by an All-Phosphorus-Based Pincer Ligand and Carbon Monoxide

PNP-pincer-stabilized iron carbonyl dihydride complexes are key intermediates in catalytic hydrogenation and dehydrogenation reactions; however, decomposition through these intermediates has been observed. This inspires the development of a PPP-pincer system that may show improved catalyst stability. In this work, bis[2-(diisopropylphosphino)phenyl]phosphine (or PP^HP) is used to react with FeCl₂ under a carbon monoxide (CO) atmosphere to yield trans-(PP^HP)Fe(CO)Cl₂. A subsequent reaction with NaBH₄ produces syn/anti-(PP^HP)FeH(CO)Cl or cis,anti-(PP^HP)Fe(CO)H₂, depending on the amount of NaBH₄ employed. The cis-dihydride complex shows catalytic activity for the conversion of PhCHO to PhCH₂OH (under H₂) or PhCO₂CH₂Ph (under Ar). It also catalyzes the dehydrogenation of PhCH₂OH to PhCHO and PhCO₂CH₂Ph, albeit with limited turnover numbers. A more efficient catalytic process is the dehydrogenation of formic acid to carbon dioxide (CO₂), which can operate under additive-free conditions. Mechanistic investigation suggests that the cis-dihydride complex undergoes protonation with formic acid to release H₂ while forming anti-(PP^HP)FeH(CO)(OCHO)·HCO₂H, in which the CO ligand has shifted and the formate is hydrogen-bonded to formic acid. The hydrido formate complex loses CO₂ under ambient conditions, completing the catalytic cycle by reforming the cis-dihydride complex.