On the Demise of PPP-Ligated Iron Catalysts in the Formic Acid Dehydrogenation Reaction

The PPP-ligated iron complexes, cis-(PP^RP)FeH₂(CO) [PP^RP = (o-Pr₂PC₆H₄)₂PR (R = H or Me)], catalyze the dehydrogenation of formic acid to carbon dioxide but lose their catalytic activity over time. This study focuses on the analysis of the species formed from the degradation of cis-(PP^MeP)FeH₂(CO) over its course of catalyzing the dehydrogenation reaction. These degradation products include species both soluble and insoluble in the reaction medium. The soluble component of the decomposed catalyst is a mixture of cis-[(PP^MeP)FeH(CO)₂][(HCO₂)(HCO₂H)], protonated PP^MeP, and oxidation products resulting from adventitious O₂. The precipitate is solvated Fe(OCHO)₂. Further mechanistic investigation suggests that cis-[(PP^MeP)FeH(CO)₂][(HCO₂)(HCO₂H)] displays diminished but measurable catalytic activity, likely through the displacement of a CO ligand by the formate ion. The formation of Fe(OCHO)₂ along with the dissociation of PP^MeP is responsible for the eventual loss of catalytic activity.