Inorganic Chemistry, Vol.54, No.7, 3325-3330, 2015
Sulfinato Iron(III) Complex for Electrocatalytic Proton Reduction
We report the first example of a sulfinato Fe(III) complex acting as a highly active electrocatalyst for proton reduction. The sulfinate binds to the metal through oxygen, resulting in a seven-membered chelate ring that is likely hemilabile during catalysis. Proton reduction occurs at -1.57 V versus Fc/Fc(+) in CH3CN with an i(c)/i(p) = 13 in CH3CN (k(obs) = 3300 s(-1)) and an overpotential of 800 mV. The catalysis is first order with respect to [catalyst] and second order with respect to [trifluoracetic acid]. An 11% increase in catalytic activity is observed in the presence of water, suggesting that sulfinate moieties are viable functional groups for aqueous proton reduction catalysts.