The Influence of OH Groups in [Fe(CO) 3 ] 2 [(μ‐ECH 2 ) 2 C(CH 2 OH) 2 ] (E = S, Se) Complexes toward the Cathodic Process

[FeFe] hydrogenase model complexes [Fe(CO) 3 ] 2 [(μ‐ECH 2 ) 2 C(CH 2 OH) 2 ] (E = S ( 1 ) or Se ( 2 )) containing CH 2 OH 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 Fe 3 (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.