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Hafnocene-based Bicyclo[2.1.1]hexene Germylenes - Formation, Reactivity, and Structural Flexibility
Zhaowen Dong1, Katja Bedbur1, Marc Schmidtmann1
1Institute of Chemistry, Carl von Ossietzky University of Oldenburg , Carl von Ossietzky-Str. 9-11, D-26129 Oldenburg, FRG, European Union.
Journal of the American Chemical Society
|January 30, 2018
Summary
New hafnocene-based germylenes were synthesized from disilylsubstituted germole dianions. These novel compounds exhibit unique electronic stabilization and structural flexibility, serving as versatile ligands for transition metals.
Area of Science:
- Organometallic Chemistry
- Main Group Chemistry
- Coordination Chemistry
Background:
- Germole dianions are versatile precursors in organometallic synthesis.
- Hafnocene complexes are known for their unique reactivity and catalytic potential.
Purpose of the Study:
- To synthesize and characterize novel hafnocene-based germylenes.
- To investigate the electronic structure and bonding in these new germylene complexes.
- To explore the potential of these germylenes as ligands in coordination chemistry.
Main Methods:
- Reaction of 2,5-disilylsubstituted germole dianions with hafnocene dichloride.
- Spectroscopic identification (NMR, UV) of intermediate hafnocene-germylene complexes.
- Complexation studies with low-valent transition metals (Fe(0), Ni(0), Au(I)) and N-heterocyclic carbenes.
Main Results:
- Successful synthesis of hafnocene-based bicyclo[2.1.1]hexene germylenes.
- Identification of intermediate hafnocene-germylene complexes.
- Demonstration of homoconjugation stabilizing the germylene.
- Exhibition of structural flexibility in complexes with various transition metals.
Conclusions:
- A new class of hafnocene-based germylenes has been developed.
- These germylenes possess unique electronic and structural properties due to homoconjugation and the hafnocene moiety.
- The observed structural adaptability makes them promising ligands for diverse transition metal complexes.
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