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Photocatalytic Oxygenation Reactions Using Water and Dioxygen
Author(s) -
Fukuzumi Shunichi,
Lee YongMin,
Nam Wonwoo
Publication year - 2019
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.201901276
Subject(s) - photocatalysis , oxygenation , chemistry , photochemistry , catalysis , organic chemistry , ecology , biology
Water (H 2 O) is the most environmentally benign reductant and is oxidized to evolve dioxygen (O 2 )—the greenest oxidant—in photosystem II. This Minireview focuses on photocatalytic oxygenation of substrates with H 2 O as an oxygen source and O 2 as an oxidant. Metal complexes can be oxidized by two molecules of one‐electron oxidants with H 2 O to produce high‐valent metal–oxo complexes, which act as active oxidants for oxygenating organic substrates. When an appropriate oxidant is employed for the substrate oxidation, the reduced oxidant can be oxidized by dioxygen to regenerate the oxidant when water and dioxygen are used as an oxygen source and an oxidant, respectively. Photoinduced electron transfer from a substrate (S) to the excited state of complex [(L)M III ] + produces a substrate radical cation (S .+ ), accompanied by the regeneration of [(L)M II ]. S .+ then reacts with H 2 O to produce an OH adduct radical that is oxidized by [(L)M III ] + to yield an oxygenated product (SO), in which the oxygen atom originates from H 2 O, accompanied by regeneration of [(L)M II ]. Photocatalytic oxidation of H 2 O by O 2 to produce H 2 O 2 is combined with the catalytic oxygenation of substrates with H 2 O 2 to produce the oxygenated products, in which the oxygen atom originates from O 2 at the beginning but later from water. This Minireview provides a promising strategy for oxygenation of substrates by using H 2 O as an oxygen source and O 2 as the greenest oxidant.