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Dehydrocoupling of alkoxyarenes with aromatic hydrosilanes catalyzed by scandium aminobenzyl complexes

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Abstract

Scandium tris(o-aminobenzyl) complex Sc(o-CH2C6H4NMe2)3 (1) and its cationic derivative [Sc(o-CH2C6H4NMe2)2][B(C6F5)4] (2) catalyze the dehydrocoupling of alkoxyarenes with various aromatic hydrosilanes in toluene at 90 °C to give C-H silylation products in 15–89% yields (24 h). The product yield depends on the nature and the ratio of the substrates, and the new carbon-silicon bond is formed only in the ortho-position relative to the alkoxy substituent in the aromatic ring. Cationic complex 2 proved to be a much more active catalyst for dehydrocoupling than neutral complex 1 and provides substrate conversion of 55–89% versus 15–45%. According to NMR spectroscopy data, complex 1 reacts with both substrates in the catalytic reaction. The reaction of 1 with anisole is accompanied by ortho-metallation of the latter and gives the complex (o-CH2C6H4NMe2)2Sc(o-C6H4OMe) (4), whereas the reaction with PhSiH3 affords the hydride [Sc(o-CH2C6H4NMe2)2H] (5). The successive reactions of 1 with [Ph3C][B(C6F5)4] and anisole (1:1:1 molar ratio) result in the formation of the cationic complex [(o-CH2C6H4NMe2)Sc(o-C6H4OMe)]+[B(C6F5)4]− (6).

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Authors and Affiliations

  1. A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 119991, Moscow, Russian Federation

    A. I. Babkin, A. A. Kissel & A. A. Trifonov

  2. G. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, 49 ul. Tropinina, 603137, Nizhny Novgorod, Russian Federation

    A. M. Ob’edkov & A. A. Trifonov

Authors
  1. A. I. Babkin
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  2. A. A. Kissel
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  3. A. M. Ob’edkov
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  4. A. A. Trifonov
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Correspondence to A. A. Trifonov.

Additional information

Dedicated to Academician of the Russian Academy of Sciences V. A. Tartakovsky on the occasion of his 90-year birthday. Based on the materials of All-Russia Conference “All-Russian Day of Rare Earths” (February 14–16, 2022, Kazan).

This study was financially supported by the Russian Science Foundation (Project No. 20-73-00304). The study was carried out using research equipment of the Center for Investigation of Molecular Structure, A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences.

No human or animal subjects were used in this research.

The authors declare no competing interests.

Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1955–1968, September, 2022.

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Babkin, A.I., Kissel, A.A., Ob’edkov, A.M. et al. Dehydrocoupling of alkoxyarenes with aromatic hydrosilanes catalyzed by scandium aminobenzyl complexes. Russ Chem Bull 71, 1955–1968 (2022). https://doi.org/10.1007/s11172-022-3614-z

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  • DOI: https://doi.org/10.1007/s11172-022-3614-z

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