Crucial Roles of a Pendant Imidazole Ligand of a Cobalt Porphyrin Complex in the Stoichiometric and Catalytic Reduction of Dioxygen
Jindou Yang, Ping Li, Xialiang Li, Lisi Xie, Ni Wang, Haitao Lei, Chaochao Zhang, Wei Zhang, Yong‐Min Lee, Weiqiang Zhang, Rui Cao, Shunichi Fukuzumi, Wonwoo Nam, Shunichi Fukuzumi, Wonwoo Nam
Abstract
Abstract A cobalt porphyrin complex with a pendant imidazole base ([(L 1 )Co II ]) is an efficient catalyst for the homogeneous catalytic two‐electron reduction of dioxygen by 1,1′‐dimethylferrocene (Me 2 Fc) in the presence of triflic acid (HOTf), as compared with a cobalt porphyrin complex without a pendant imidazole base ([(L 2 )Co II ]). The pendant imidazole ligand plays a crucial role not only to provide an imidazolinium proton for proton‐coupled electron transfer (PCET) from [(L 1 )Co II ] to O 2 in the presence of HOTf but also to facilitate electron transfer (ET) from [(L 1 )Co II ] to O 2 in the absence of HOTf. The kinetics analysis and the detection of intermediates in the stoichiometric and catalytic reduction of O 2 have provided clues to clarify the crucial roles of the pendant imidazole ligand of [(L 1 )Co II ] for the first time.