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The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
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Alkene isomerisation catalysed by a ruthenium PNN pincer complex
Sébastien Perdriau1, Mu-Chieh Chang, Edwin Otten
1Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG Groningen (The Netherlands), Fax: (+31) 50-3634296.
Chemistry (Weinheim an Der Bergstrasse, Germany)
|September 30, 2014
Summary
This study reveals a new ruthenium pincer complex that isomerizes alkenes under mild conditions. Alcohol activation facilitates a mechanism involving alkoxide complex formation and hemilabile arm dissociation for efficient alkene insertion.
Area of Science:
- Organometallic Chemistry
- Catalysis
- Organic Synthesis
Background:
- Pincer complexes offer unique catalytic properties due to their tridentate coordination.
- Alkene isomerization is a fundamental transformation in organic chemistry with broad applications.
- Ruthenium complexes are versatile catalysts for various organic reactions.
Purpose of the Study:
- To investigate the alkene isomerization capabilities of a dearomatised [Ru(CO)H(PNN)] pincer complex.
- To elucidate the mechanism of alcohol-activated alkene isomerization.
- To characterize novel ruthenium complexes formed during the reaction.
Main Methods:
- Synthesis and characterization of the [Ru(CO)H(PNN)] pincer complex.
- Variable-temperature Nuclear Magnetic Resonance (VT NMR) spectroscopy to study reaction mechanisms.
- Alkene isomerization reaction studies under varying conditions.
- Characterization of a new Ru(0) coordination complex.
Main Results:
- The [Ru(CO)H(PNN)] pincer complex effectively isomerizes alkenes under mild conditions upon alcohol activation.
- VT NMR studies support a mechanism involving rearomatised alkoxide complex formation.
- Hemilabile dissociation of the diethylamino arm enables cis-alkene binding and insertion into the Ru-H bond.
- A novel, uncommon Ru(0) coordination complex was successfully synthesized and characterized.
Conclusions:
- Alcohol activation is crucial for the catalytic activity of the dearomatised pincer complex in alkene isomerization.
- The hemilabile nature of the PNN ligand plays a key role in the catalytic cycle.
- The study expands the scope of ruthenium-catalyzed alkene isomerization reactions.
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