1-Aza-2,4-disilabicyclo[1.1.0]butanes with Superelongated C-N σ-Bonds

Jiancheng Li; Daniel J Goffitzer; Meiyu Xiang; Yilin Chen; Wenjun Jiang; Martin Diefenbach; Hongping Zhu; Max C Holthausen; Herbert W Roesky

doi:10.1021/jacs.1c03149

1-Aza-2,4-disilabicyclo[1.1.0]butanes with Superelongated C-N σ-Bonds

J Am Chem Soc. 2021 Jun 9;143(22):8244-8248. doi: 10.1021/jacs.1c03149. Epub 2021 May 26.

Authors

Jiancheng Li¹, Daniel J Goffitzer², Meiyu Xiang¹, Yilin Chen¹, Wenjun Jiang¹, Martin Diefenbach², Hongping Zhu¹, Max C Holthausen², Herbert W Roesky³

Affiliations

¹ State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China.
² Institut für Anorganische und Analytische Chemie, Goethe-Universität Frankfurt, Max-von-Laue-Straße 7, 60438 Frankfurt am Main, Germany.
³ Institut für Anorganische Chemie, Georg-August-Universität, 37077 Göttingen, Germany.

PMID: 34037391
DOI: 10.1021/jacs.1c03149

Abstract

Two silylene molecules oxidatively react under formal [1 + 2 + 1]-cycloaddition to the C≡N bond of nitriles to yield 1-aza-2,4-disilabicyclo[1.1.0]butanes (L)(Cl)Si[μ-η^1,2-NC(p-RC₆H₄)]Si(Cl)(L) (L = PhC(NtBu)₂, R = CF₃ (2), F (3), Cl (4), Br (5)). The strongly folded bicyclic SiCNSi cores in 2-5 feature inverted bridgehead carbon atoms and superelongated C-N bonds [1.745(12) to 1.801(2) Å], exceeding the lengths of C-N single bonds in known silaaziridines by up to 23%. Detailed bonding analysis discloses C-N bonding interactions, sharing far-reaching similarities with the central C-C bond in [1.1.1]propellane.