A stable cyclic (silyl)(thia)silylene via stepwise cycloaddition
John C Johnson1, Yuzhong Wang1, Pingrong Wei1
1Department of Chemistry and the Center for Computational Chemistry, The University of Georgia, Athens, Georgia 30602-2556, USA. robinson@uga.edu.
Researchers synthesized a novel carbene-stabilized cyclic (silyl)(thia)silylene compound. This was achieved through a unique cycloaddition reaction involving a disilicon(0) species and an imidazole-based dithione dimer.
Area of Science:
- Organosilicon Chemistry
- Main Group Chemistry
- Synthetic Chemistry
Background:
- Dithione dimers are versatile precursors in inorganic synthesis.
- Carbene-stabilized silicon compounds offer unique reactivity.
- Cycloaddition reactions are fundamental in constructing complex ring systems.
Purpose of the Study:
- To explore the reactivity of carbene-stabilized disilicon(0) with dithiones.
- To synthesize and characterize novel silicon-containing heterocyclic compounds.
- To elucidate the reaction mechanism of the cycloaddition.
Main Methods:
- Low-temperature reaction of imidazole-based dithione dimer (1) with carbene-stabilized disilicon(0) (2).
- 1:1 molar ratio reaction conditions.
- Computational studies to investigate the reaction pathway.
Main Results:
- Formation of a carbene-stabilized cyclic (silyl)(thia)silylene (3).
- Integration of a dithiolene unit (C2S2) into a C2S2Si2 six-membered ring.
- Evidence for an unprecedented stepwise [4 + 2]-like cycloaddition mechanism.
Conclusions:
- A novel C2S2Si2 heterocyclic compound was successfully synthesized.
- The reaction proceeds via a unique cycloaddition pathway involving Si=Si and dithione moieties.
- This study expands the scope of silicon-based heterocycle synthesis.
Related Concept Videos
Cycloaddition Reactions: Overview
[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction
Diels–Alder Reaction Forming Cyclic Products: Stereochemistry
Diels–Alder Reaction Forming Bridged Bicyclic Products: Stereochemistry
Cycloaddition Reactions: MO Requirements for Thermal Activation
Electrophilic 1,2- and 1,4-Addition of X2 to 1,3-Butadiene


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