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Synthesis of Hypervalent Iodonium Alkynyl Triflates for the Application of Generating Cyanocarbenes
Published on: September 8, 2013
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Synthesis and Reactivity of Tricoordinate Organoberyllium Azides
Corinna Czernetzki1,2, Tanja Kunz1,2, Silvia Huynh1,2
1Institute for Inorganic Chemistry, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.
Angewandte Chemie (International Ed. in English)
|March 12, 2024
Summary
Novel beryllium azide complexes were synthesized and studied. Their reactions reveal ligand scrambling, nitrene insertion into beryllium-carbon bonds, and unexpected ligand exchange with N-heterocyclic carbenes.
Area of Science:
- Organometallic Chemistry
- Inorganic Synthesis
- Coordination Chemistry
Background:
- Tricoordinate beryllium complexes are rare and their reactivity is underexplored.
- Azidoberyllium compounds offer unique synthetic pathways due to the azide group's versatility.
Purpose of the Study:
- To synthesize and characterize novel terminal mono- and disubstituted beryllium azides.
- To investigate the reactivity of these complexes under thermolysis and photolysis conditions.
- To explore reactions with N-heterocyclic carbenes and boroles.
Main Methods:
- Synthesis of beryllium azide complexes using bulky N-heterocyclic ligands.
- Characterization via Nuclear Magnetic Resonance (NMR) spectroscopy and X-ray crystallography.
- Thermolysis and photolysis studies to determine reaction products.
Main Results:
- Successful synthesis of [(CAAC)Be(N3)R] and [L2Be(N3)2] complexes.
- Evidence of ligand scrambling and nitrene insertion into the CAAC-Be bond, forming cyclic alkyl(amino)imine (CAAI) ligands.
- Observation of CAAC-NHC ligand exchange and the formation of a γ-azide adduct with pentaphenylborole.
Conclusions:
- The study presents the first examples of tricoordinate azidoberyllium complexes.
- These complexes exhibit unique reactivity, including ligand scrambling and insertion reactions.
- The findings open new avenues for synthesizing heterocyclic compounds.
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