A Linear C=Ge=C Heteroallene with a Di‐coordinated Germanium Atom**
- 8 May 2023
- journal article
- research article
- Published by Wiley in Angewandte Chemie International Edition
- Vol. 62 (24) , e202302836
Abstract
Allenes (>C=C=C<) are classified as cumulated dienes with a linear structure and an sp ‐hybridized central carbon atom. We have synthesized and isolated a stable 2‐germapropadiene with bulky silyl substituents. The 2‐germapropadiene allene moiety adopts a linear structure both in the solid state and in solution. An X‐ray diffraction electron‐density‐distribution (EDD) analysis of this 2‐germapropadiene confirmed the linear C=Ge=C geometry with a formally sp ‐hybridized germanium atom that bears two orthogonal C=Ge π‐bonds. Based on detailed structural and computational studies, we concluded that the linear geometry of the isolated 2‐germapropadiene most likely arises from the negative hyperconjugation of the silyl substituents at the terminal carbon atoms. The 2‐germapropadiene reacts rapidly with nucleophiles, indicating that the linearly oriented germanium atom is highly electrophilic.Keywords
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Funding Information
- Japan Society for the Promotion of Science (JP18K14204)
- Japan Society for the Promotion of Science (JP20K05468)
This publication has 57 references indexed in Scilit:
- Acyclic Germylones: Congeners of Allenes with a Central Germanium AtomJournal of the American Chemical Society, 2013
- A Cyclic Silylone (“Siladicarbene”) with an Electron‐Rich Silicon(0) AtomAngewandte Chemie International Edition, 2013
- Sn[Si(SiMe3)3]3− and Sn3[Si(SiMe3)3]4: first insight into the mechanism of the disproportionation of a tin monohalide gives access to the shortest double bond of tinChemical Communications, 2010
- Trigermaallene and 1,3-DigermasilaalleneOrganometallics, 2004
- A stable silicon-based allene analogue with a formally sp-hybridized silicon atomNature, 2003
- GERMANIUM ORGANOMETALLIC COMPOUNDS: CLASSIFICATION AND ANALYSIS OF CRYSTALLOGRAPHIC AND STRUCTURAL DATAMain Group Metal Chemistry, 2002
- Acetylene-Linked Bis(germaethenes): The First Molecules with Conjugated Germanium−Carbon Double Bonds1Organometallics, 2000
- Tetrasupersilyl-tristannaallene and -tristannacyclopropene (tBu3Si)4Sn3 – Isomers with the Shortest Sn=Sn Double Bonds to DateEuropean Journal of Inorganic Chemistry, 1999
- Syntheses and reactions of substituent stabilized thione methylidesJournal of the American Chemical Society, 1976
- Polylithium compounds. III. Polylithium compounds from propyne and 1-butyne, and their polysilicon derivativesJournal of the American Chemical Society, 1969