4.7 Article

An NAD+-type earth-abundant metal complex enabling photo-driven alcohol oxidation

Journal

CHEMICAL COMMUNICATIONS
Volume 57, Issue 99, Pages 13574-13577

Publisher

ROYAL SOC CHEMISTRY
DOI: 10.1039/d1cc04665a

Keywords

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Funding

  1. Ministry of Education, Culture, Sports, Science, and Technology (MEXT) [JP20H05095, JP17K05806]
  2. Japan Society for the Promotion of Science (JSPS)

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The study discovered an NAD(+)-type metal complex with oxidizing ability to convert alcohols to aldehydes and ketones, and successfully synthesized a novel zinc(II) complex with a C-C coupling ligand. Kinetic analysis based on absorption spectroscopic measurements revealed that the reaction proceeds through electron transfer followed by proton transfer mechanism.
For the first time, an NAD(+)-type earth-abundant metal complex [Zn(pbn)(2)(H2O)](ClO4)(2) (1) was found to exhibit photo-induced oxidizing ability to convert various primary and secondary alcohols to the corresponding aldehyde and ketone compounds. In addition, a two-electron-reduced Zn(II) complex [Zn(pbnH-pbnH)(ClO4)(2)] (1(red)) comprising the novel C-C coupling ligand, obtained by the photo-induced oxidation of alcohols by 1, was successfully isolated and completely characterized. We clarified that the photochemical oxidation of alcohols by 1 to produce 1(r)(ed) proceeds via an electron transfer followed by proton transfer mechanism as elucidated by kinetic analysis on the basis of absorption spectroscopic measurements.

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