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Cercosporin-Photocatalyzed [4+1]- and [4+2]-Annulations of Azoalkenes Under Mild Conditions
Published on: July 17, 2020
Scandium Reduced Arene Complex: Protonation and Reaction with Azobenzene
Priyabrata Ghana1, Thomas P Spaniol1, Jun Okuda1
1Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, 52056, Aachen, Germany.
Abstract:
The reactivity of the reduced anthracene complex of scandium [Li(thf)3 ][Sc{N(tBu)Xy}2 (anth)] (2-anth-Li) (Xy=3,5-Me2 C6 H3 ; anth=C14 H10 2- , thf=tetrahydrofuran) toward Brønsted acid [NEt3 H][BPh4 ] and azobenzene is reported. While a stepwise protonation of 2-anth-Li with two equivalents of [NEt3 H][BPh4 ] afforded the scandium cation [Sc{N(tBu)Xy}2 (thf)2 ][BPh4 ] (3), reduction of azobenzene gave a thermolabile, anionic scandium reduced azobenzene complex [Li(thf)][Sc{N(tBu)Xy}2 (η2 -PhNNPh)] (4), which slowly lost one of the anilide ligands to form the neutral scandium azobenzene complex dimer [Sc{N(tBu)Xy}(μ-η2 :η2 -Ph2 N2 )]2 (5). Exposure of 3 to CO2 produced the scandium carbamate complex [Sc{κ2 -O2 CN(tBu)(Xy)}2 ][BPh4 ] (6) as a result of CO2 insertion into the Sc-N bonds. In an attempt to prepare scandium hydrides, the reaction of 3 with the hydride sources LiAlH4 and Na[BEt3 H] led to the terminal aluminum hydride [AlH{N(tBu)Xy}2 (thf)] (7) and the scandium n-butoxide [Sc{N(tBu)(Xy)}2 (μ-OnBu)] (8) after Sc/Al transmetalation and nucleophilic ring-opening of THF, respectively. All reported compounds isolated in moderate to good yields were fully characterized.
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