title: Sulfinato iron(III) complex for electrocatalytic proton reduction.
abstract: 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 ic/ip = 13 in CH3CN (kobs = 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.
authors: †Department of Chemistry, College of William and Mary, 540 Landrum Drive, Williamsburg, Virginia 23185, United States.
authors: Andrew C
authors: AC
authors: Cavell
authors: †Department of Chemistry, College of William and Mary, 540 Landrum Drive, Williamsburg, Virginia 23185, United States.
authors: Carolyn L
authors: CL
authors: Hartley
authors: †Department of Chemistry, College of William and Mary, 540 Landrum Drive, Williamsburg, Virginia 23185, United States.
authors: Dan
authors: D
authors: Liu
authors: †Department of Chemistry, College of William and Mary, 540 Landrum Drive, Williamsburg, Virginia 23185, United States.
authors: Connor S
authors: CS
authors: Tribble
authors: †Department of Chemistry, College of William and Mary, 540 Landrum Drive, Williamsburg, Virginia 23185, United States.
authors: William R
authors: WR
authors: McNamara