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[FeFe] hydrogenase model complexes [Fe(CO)₃]₂[(μ‐ECH₂)₂C(CH₂OH)₂] (E = S (1) or Se (2)) containing CH₂OH bridgehead substituents were synthesized via reaction of equimolar amounts of 4, 4‐bis(hydroxymethyl)‐1, 2‐dithiolane (A) or 4, 4‐bis(hydroxymethyl)‐1, 2‐diselenolane (B) with Fe₃(CO)₁₂ in toluene at 100 °C. The presence of OH groups in complexes 1 and 2 is found to influence the cathodic processes and their potentials. The catalytic reduction of acetic acid (AcOH) occurs by the anions 1^– and 2^–, while the neutral complexes are procatalysts.