Bis(2-diisopropylphosphinophenyl)phosphine (or iPrPPHP) ligated iron complexes, trans-(iPrPPHP)Fe(CO)Cl2, (iPrPPHP)FeH(CO)Cl and cis,anti-(iPrPPHP)Fe(CO)H2 have been synthesized. Among these complexes, cis,anti-(iPrPPHP)Fe(CO)H2 catalyzes additive-free formic acid dehydrogenation to yield dihydrogen and carbon dioxide. Mechanistic study suggests that the cis,anti dihydride complex undergoes protonation with formic acid to form the anti-(iPrPPHP)FeH(CO)(OCHO)HCO2H complex as an intermediate which spontaneously releases carbon dioxide at ambient temperature to complete the catalytic cycle by reforming the cis,anti dihydride complex.

Additive-free dehydrogenation of formic acid using an iron catalyst

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