Electrocatalytic proton reduction by thiolate-capped triiron clusters [Fe3(CO)9(μ3-SR)(μ-H)] (R = iPr, tBu)

TY - JOUR

T1 - Electrocatalytic proton reduction by thiolate-capped triiron clusters [Fe3(CO)9(μ3-SR)(μ-H)] (R = iPr, tBu)

AU - Ghosh, Shishir

AU - Basak-Modi, Sucharita

AU - Richmond, Michael G.

AU - Nordlander, Ebbe

AU - Hogarth, Graeme

PY - 2018/4/30

Y1 - 2018/4/30

N2 - The redox behaviour and electrocatalytic proton reduction ability of the thiolate-capped triiron clusters [Fe3(CO)9(μ3-SR)(μ-H)] (1, R = iPr; 2, R= tBu) have been investigated. In CH2Cl2, both show a quasi-reversible reduction and an irreversible oxidation. The thiol substituent has a significant influence on their reduction potentials (E1/2 = –1.24 V for 1 and E1/2 = –1.40 V for 2 vs. Fc+/Fc) but less impact on oxidation potentials (E1/2 = 0.99 V for 1 and E1/2 = 0.93 V for 2 vs. Fc+/Fc). Reduction is quasi-reversible and DFT studies reveal that this is due to scission of an iron-iron bond. While the clusters are not protonated by CF3CO2H or HBF4·Et2O, they can catalyse proton reduction of these acids at their corresponding reduction potentials following an ECEC mechanism.

AB - The redox behaviour and electrocatalytic proton reduction ability of the thiolate-capped triiron clusters [Fe3(CO)9(μ3-SR)(μ-H)] (1, R = iPr; 2, R= tBu) have been investigated. In CH2Cl2, both show a quasi-reversible reduction and an irreversible oxidation. The thiol substituent has a significant influence on their reduction potentials (E1/2 = –1.24 V for 1 and E1/2 = –1.40 V for 2 vs. Fc+/Fc) but less impact on oxidation potentials (E1/2 = 0.99 V for 1 and E1/2 = 0.93 V for 2 vs. Fc+/Fc). Reduction is quasi-reversible and DFT studies reveal that this is due to scission of an iron-iron bond. While the clusters are not protonated by CF3CO2H or HBF4·Et2O, they can catalyse proton reduction of these acids at their corresponding reduction potentials following an ECEC mechanism.

KW - Triiron clusters

KW - Thiolate

KW - Electrocatalytic proton reduction

KW - DFT studies

U2 - 10.1016/j.ica.2018.04.034

DO - 10.1016/j.ica.2018.04.034

M3 - Article

SN - 0020-1693

JO - INORGANICA CHIMICA ACTA

JF - INORGANICA CHIMICA ACTA

ER -