Taming Heavier Group 14 Imine Analogues: Accessing Tin Nitrogen [Sn=N] Double Bonds and their Cycloaddition/Metathesis Chemistry.

Autor: Fischer M; Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford, OX1 3QR, UK., Roy MMD; Department of Chemistry, Catalysis Research Center and Institute for Silicon Chemistry, Technische Universität München, 85748, Garching bei München, Germany., Wales LL; Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford, OX1 3QR, UK., Ellwanger MA; Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford, OX1 3QR, UK., McManus C; Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford, OX1 3QR, UK., Roper AF; Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford, OX1 3QR, UK., Heilmann A; Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford, OX1 3QR, UK., Aldridge S; Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford, OX1 3QR, UK.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2022 Nov 25; Vol. 61 (48), pp. e202211616. Date of Electronic Publication: 2022 Oct 25.
DOI: 10.1002/anie.202211616
Abstrakt: A systematic study to access stable stannaimines is reported, by combining different heteroleptic stannylenes with a range of organic azides. The reactions of terphenyl-/hypersilyl-substituted stannylenes yield the putative tin nitrogen double bond, but is directly followed by 1,2-silyl migration to give Sn II systems featuring bulky silylamido ligands. By contrast, the transition from a two σ donor ligand set to a mixed σ-donor/π-donor scaffold allows access to three new stannaimines which can be handled at room temperature. The reactivity profile of these Sn=N bonded species is crucially dependent on the substituent at the nitrogen atom. As such, the Sn=NMes (Mes=2,4,6-Me 3 C 6 H 2 ) system is capable of activating a broad range of substrates under ambient conditions via 1,2-addition reactions, [2+2] and [4+2] cycloaddition reactions. Most interestingly, very rare examples of main group multiple bond metathesis reactions are also found to be viable.
(© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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