The Influence of OH Groups in [Fe(CO)3]2[(μ‐ECH2)2C(CH2OH)2] (E = S, Se) Complexes toward the Cathodic Process

Abstract

Abstract[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.