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10:51
The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
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Intermolecular Dehydrative Coupling and Intramolecular Cyclization of Ruthenium Vinylidene Complexes Formed from
Pi-Yeh Chia1, Cheng-Chen Kuo1, Shou-Ling Huang1
1Department of Chemistry, National (Taiwan) University, Taipei, 106, Taiwan.
Chemistry, an Asian Journal
|October 7, 2018
Summary
This study reveals a novel intermolecular dehydrative coupling reaction forming C-C bonds in vinylidene complexes. The research demonstrates the synthesis of dinuclear bisvinylidene complexes and explores factors influencing these reactions, including functional groups and reaction conditions.
Area of Science:
- Organometallic Chemistry
- Synthetic Organic Chemistry
- Catalysis
Background:
- Vinylidene complexes are versatile intermediates in organometallic chemistry.
- Dehydrative coupling reactions offer efficient pathways for C-C bond formation.
- Understanding substituent effects is crucial for controlling reactivity and product selectivity.
Purpose of the Study:
- To investigate a novel intermolecular dehydrative coupling reaction involving vinylidene complexes.
- To synthesize dinuclear bisvinylidene complexes and explore their formation mechanisms.
- To evaluate the influence of various functional groups and reaction conditions on the coupling process.
Main Methods:
- Reaction of ortho-alkynyl benzaldehydes and ketones with a Ruthenium catalyst ([Ru]-Cl, where [Ru] = Cp(PPh3)2Ru).
- Cyclization reactions under varying conditions (e.g., solvent, temperature, additives).
- Characterization of products using spectroscopic methods (NMR, IR) and X-ray crystallography.
Main Results:
- A novel intermolecular dehydrative coupling reaction forming a C-C bond was discovered, yielding dinuclear bisvinylidene complexes.
- The presence of a fluoro group on the aryl ring inhibited the coupling reaction.
- Intramolecular dehydration pathways were observed for ketone-containing substrates, leading to different product classes (e.g., isochromenes, 1-benzosuberones).
Conclusions:
- The study successfully demonstrated a new synthetic route to dinuclear bisvinylidene complexes via intermolecular coupling.
- Substituent effects significantly impact the reaction outcome, favoring intermolecular coupling with electron-donating groups and intramolecular pathways with ketones.
- The findings provide valuable insights into the reactivity of vinylidene complexes and offer pathways for designing new organometallic transformations.
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