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![[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59739.jpg&w=3840&q=50)
[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst
Published on: May 21, 2019
Study of the Air-Tolerant 1,3-Diphosphacyclobutane-2,4-diyl through the Direct Arylation
1Department of Chemical Science and Engineering, School of Material and Chemical Technology, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro, Tokyo, 152-8552, Japan.
Abstract:
Installing π-functional substituents on the skeletal phosphorus atoms of the air-tolerant 1,3-diphosphacyclobutane-2,4-diyl unit are promising for tuning the open-shell singlet P-heterocyclic chromophore. The sterically encumbered 1,3-diphosphaCycloButen-4-yl Anion (CBA), generated from the phosphorus-carbon triple bond, was available for the regioselective arylation via nucleophilic aromatic substitution (SN Ar) reaction, addition to arynes, and single-electron transfer (SET) process affording the corresponding P-arylated 1,3-diphosphacyclobutane-2,4-diyls. The photo-absorption and redox properties correlated with the effects of the aryl substituents on the 1,3-diphosphacyclobutane-2,4-diyl unit. The X-ray analyses enabled not only to discuss the metric parameters but also to visualize the radicalic electrons via the electron-density distribution analysis. The electron-donating character of the P-heterocyclic chromophores induced the p-type semiconductor behavior. Detection of hydrogen fluoride via formation of the 1λ5 ,3λ5 -diphosphete derivative was also developed.
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