Synthesis and Reactivity of Acyclic Germanimines: Silyl Rearrangement and Cycloadditions
Authors:
- 14 May 2021
- journal article
- research article
- Published by American Chemical Society (ACS) in Inorganic Chemistry
- Vol. 60 (11) , 8293-8303
Abstract
We report the synthesis of aromatic germanimines [(HMDS)2Ge═NAr] (Ar = Ph, Mes, Dipp; Mes = 2,4,6-Me3C6H2, Dipp = 2,6-iPr2C6H3) and an investigation into their associated reactivity. [(HMDS)2Ge═NPh] decomposes above −30 °C, while [(HMDS)2Ge═NDipp] engages in an intramolecular reaction at 60 °C. [(HMDS)2Ge═NMes] was shown to rearrange via a 1,3-silyl migration to give [(HMDS){(SiMe3)(Mes)N}Ge(NSiMe3)] in a 1:7 equilibrium mixture at room temperature. These latter germanimines react with unsaturated polar substrates such as CO2, ketones, and arylisocyanate via a [2 + 2] cycloaddition pathway.Keywords
This publication has 73 references indexed in Scilit:
- Main Group Multiple Bonds for Bond Activations and CatalysisChemistry – A European Journal, 2020
- An Update on Multiple Bonding between Heavier Main Group Elements: The Importance of Pauli Repulsion, Charge-Shift Character, and London Dispersion Force EffectsOrganometallics, 2020
- Reactivity in the periphery of functionalised multiple bonds of heavier group 14 elementsChemical Society Reviews, 2015
- π-Bonding and the Lone Pair Effect in Multiple Bonds between Heavier Main Group ElementsChemical Reviews, 1999
- Organoimido Complexes of the Transition Metals1994
- Transition metal imido complexesJournal of the American Chemical Society, 1992
- Multiply bonded germanium species. Recent developmentsChemical Reviews, 1990
- Reaktionen von Germylenen mit Aziden: Iminogermane, Azidogermane, Tetrazagermole und HexaazadigermadispirododecaneEuropean Journal of Inorganic Chemistry, 1989
- A stable and long-lived germaimineTetrahedron Letters, 1987
- Germa-2 azetidines: precurseurs des premieres germaiminesJournal of Organometallic Chemistry, 1978