TY - JOUR
T1 - A Non-Heme Diiron Complex for (Electro)catalytic Reduction of Dioxygen
T2 - Tuning the Selectivity through Electron Delivery
AU - Wang, Lianke
AU - Gennari, Marcello
AU - Cantú Reinhard, Fabián G.
AU - Gutiérrez, Javier
AU - Morozan, Adina
AU - Philouze, Christian
AU - Demeshko, Serhiy
AU - Artero, Vincent
AU - Meyer, Franc
AU - de Visser, Sam P.
AU - Duboc, Carole
PY - 2019/5/22
Y1 - 2019/5/22
N2 - In the oxygen reduction reaction (ORR) domain, the investigation of new homogeneous catalysts is a crucial step toward the full comprehension of the key structural and/or electronic factors that control catalytic efficiency and selectivity. Herein, we report a unique non-heme diiron complex that can act as a homogeneous ORR catalyst in acetonitrile solution. This iron(II) thiolate dinuclear complex, [FeII2(LS)(LSH)] ([Fe2SH]+) (LS2- = 2,2'-(2,2'-bipyridine-6,6'-diyl)bis(1,1-diphenylethanethiolate)) contains a thiol group in the metal coordination sphere. [Fe2SH]+ is an efficient ORR catalyst both in the presence of a one-electron reducing agent and under electrochemically assisted conditions. However, its selectivity is dependent on the electron delivery pathway; in particular, the process is selective for H2O2 production under chemical conditions (up to ∼95%), whereas H2O is the main product during electrocatalysis (less than ∼10% H2O2). Based on computational work alongside the experimental data, a mechanistic proposal is discussed that rationalizes the selective and tunable reduction of dioxygen.
AB - In the oxygen reduction reaction (ORR) domain, the investigation of new homogeneous catalysts is a crucial step toward the full comprehension of the key structural and/or electronic factors that control catalytic efficiency and selectivity. Herein, we report a unique non-heme diiron complex that can act as a homogeneous ORR catalyst in acetonitrile solution. This iron(II) thiolate dinuclear complex, [FeII2(LS)(LSH)] ([Fe2SH]+) (LS2- = 2,2'-(2,2'-bipyridine-6,6'-diyl)bis(1,1-diphenylethanethiolate)) contains a thiol group in the metal coordination sphere. [Fe2SH]+ is an efficient ORR catalyst both in the presence of a one-electron reducing agent and under electrochemically assisted conditions. However, its selectivity is dependent on the electron delivery pathway; in particular, the process is selective for H2O2 production under chemical conditions (up to ∼95%), whereas H2O is the main product during electrocatalysis (less than ∼10% H2O2). Based on computational work alongside the experimental data, a mechanistic proposal is discussed that rationalizes the selective and tunable reduction of dioxygen.
UR - http://www.scopus.com/inward/record.url?scp=85067634614&partnerID=8YFLogxK
U2 - 10.1021/jacs.9b02011
DO - 10.1021/jacs.9b02011
M3 - Article
C2 - 31026148
AN - SCOPUS:85067634614
SN - 0002-7863
VL - 141
SP - 8244
EP - 8253
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 20
ER -