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Cyclopentadienyl Cobalt Complexes as Precatalysts for Electrocatalytic Hydrogen Evolution
Author(s) -
Waldie Kate M.,
Kim SungKwan,
Ingram Andrew J.,
Waymouth Robert M.
Publication year - 2017
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201700188
Subject(s) - chemistry , electrocatalyst , cobalt , catalysis , cyclopentadienyl complex , electrochemistry , acetonitrile , denticity , inorganic chemistry , ligand (biochemistry) , organic chemistry , metal , electrode , biochemistry , receptor
Electrocatalytic hydrogen evolution is reported with a series of dicationic cobalt complexes [CpCo(N ^ N)(CH 3 CN)](ClO 4 ) 2 (Cp = cyclopentadienyl; N ^ N = bipyridine, pyrazolylpyridine, phenylazopyridine) using N , N ‐dimethylformamidinium buffer as the proton source in acetonitrile. The catalytic current profiles obtained for each complex are very similar to each other with overpotentials ranging from 1.2 to 1.4 V, which suggests a common active catalytic species. Further electrochemical studies demonstrate that these complexes are unstable under electrocatalytic conditions: the bidentate nitrogen ligand is readily lost upon reduction in the presence of acid, initially generating [CpCo(CH 3 CN) 3 ] + , which undergoes further decomposition to surface‐adsorbed species that are responsible for the observed electrocatalysis.