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Scandium Reduced Arene Complex: Protonation and Reaction with Azobenzene.

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.

SUBMITTER: Ghana P

PROVIDER: S-EPMC8596697 | biostudies-literature |

REPOSITORIES: biostudies-literature

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