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![[(DPEPhos)(bcp)Cu]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)
[(DPEPhos)(bcp)Cu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst
Published on: May 21, 2019
A Vicinal Electrophilic Diborylation Reaction Furnishes Doubly Boron-Doped Polycyclic Aromatic Hydrocarbons
Alexandra John1, Michael Bolte1, Hans-Wolfram Lerner1
1Institut für Anorganische Chemie, Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, 60438, Frankfurt am Main, Germany.
Abstract:
Ten examples of unsymmetrically benzannulated, boron-doped polycyclic aromatic hydrocarbons (B-PAHs) were prepared by a one-pot protocol using 4,5-dichloro-1,2-bis(trimethylsilyl)benzene (1), BBr3 , and selected PAHs-among them anthracene, benzo[a]pyrene, biphenylene, and fluoranthene. After mesitylation at the boron centers, the resulting air- and water-stable products were investigated by 1 H/11 B{1 H}/13 C{1 H} NMR spectroscopy, X-ray crystallography, cyclic voltammetry, and UV/Vis absorption/emission spectroscopy. The experiments were augmented by DFT calculations. Most of the B-PAHs are brightly luminescent (ΦPL up to 90 %) and undergo reversible reduction at moderate half-wave potentials. The two chloro substituents of 1 are not only mandatory for accomplishing efficient diborylation, but can subsequently be used for Stille-type coupling reactions to introduce 2-thienyl moieties. Alternatively, Cl/H exchange is achievable with HSiEt3 in a quantitative, Pd-catalyzed transformation.
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