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Further Investigation of a Nickel‐Based Homogeneous Water Oxidation Catalyst with Two cis Labile Sites
Author(s) -
Luo GangYi,
Huang HaiHua,
Wang JiaWei,
Lu TongBu
Publication year - 2016
Publication title -
chemsuschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.412
H-Index - 157
eISSN - 1864-564X
pISSN - 1864-5631
DOI - 10.1002/cssc.201501474
Subject(s) - chemistry , catalysis , nickel , intramolecular force , molecule , medicinal chemistry , electrochemistry , hydrogen peroxide , ligand (biochemistry) , reaction mechanism , peroxide , homogeneous catalysis , aqueous solution , inorganic chemistry , stereochemistry , organic chemistry , biochemistry , receptor , electrode
The reaction of N , N′ ‐dimethyl‐ N , N′ ‐bis(pyridin‐2‐ylmethyl)‐1,2‐diaminoethane ligand (L) with Ni(ClO 4 ) 2 ⋅6 H 2 O generated a complex of [NiL(H 2 O) 2 ](ClO 4 ) 2 ( 1 ) with two cis labile sites occupied by two coordinated H 2 O molecules, which can homogeneously electrocatalyze water oxidation in pH 6.5 acetate (OAc − ) buffer at room temperature. The catalytic mechanism was studied by electrochemical experiments and density functional theory calculations to elucidate the following steps: (a) one of two water molecules in 1 is exchanged by OAc − to generate [NiL(H 2 O)(OAc)] + when dissolved in OAc − buffer, (b) Ni II is directly oxidized to Ni IV and OAc − is replaced with OH − to form [Ni IV L(OH) 2 ] 2+ , and (c) a peroxide intermediate is formed through the intramolecular O−O coupling in the presence of OAc − , which undergoes further oxidation to release O 2 .