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 - 2018/8/1
Y1 - 2018/8/1
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 - DFT studies
KW - Electrocatalytic proton reduction
KW - Thiolate
KW - Triiron clusters
UR - http://www.scopus.com/inward/record.url?scp=85047102704&partnerID=8YFLogxK
U2 - 10.1016/j.ica.2018.04.034
DO - 10.1016/j.ica.2018.04.034
M3 - Article
AN - SCOPUS:85047102704
SN - 0020-1693
VL - 480
SP - 47
EP - 53
JO - Inorganica Chimica Acta
JF - Inorganica Chimica Acta
ER -