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Updated: May 16, 2026

Imine Metathesis by Silica-Supported Catalysts Using the Methodology of Surface Organometallic Chemistry
Published on: October 18, 2019
Efficient metathesis of terminal alkynes.
Birte Haberlag1, Matthias Freytag, Constantin G Daniliuc
1Institut für Anorganische und Analytische Chemie, Technische Universität Braunschweig, Germany.
New trimethylbenzylidyne complexes featuring molybdenum and tungsten were synthesized. The molybdenum complex efficiently catalyzes alkyne and diyne metathesis reactions at room temperature with low catalyst loading.
Area of Science:
- Organometallic Chemistry
- Catalysis
- Organic Synthesis
Background:
- Alkyne metathesis is a crucial reaction in organic synthesis.
- Development of efficient catalysts for alkyne metathesis remains an active research area.
- Terminal alkynes present unique challenges in metathesis reactions.
Purpose of the Study:
- To synthesize novel 2,4,6-trimethylbenzylidyne complexes of molybdenum and tungsten.
- To evaluate the catalytic activity of the synthesized molybdenum complex in alkyne metathesis.
- To investigate the efficacy of the catalyst for both internal and terminal alkyne transformations.
Main Methods:
- Synthesis of molybdenum and tungsten complexes from metal carbonyl precursors.
- Characterization of the synthesized organometallic compounds.
- Testing the catalytic performance in various alkyne metathesis reactions.
Main Results:
- Successful synthesis of the 2,4,6-trimethylbenzylidyne complexes [MesC≡M{OC(CF(3))(2)Me}(3)] (M=Mo, W).
- The molybdenum complex demonstrated high efficiency as a catalyst for internal and terminal alkyne metathesis.
- Effective catalysis was also observed for ring-closing metathesis of internal and terminal α,ω-diynes.
- The reactions proceeded at room temperature with low catalyst concentrations.
Conclusions:
- The novel molybdenum complex is a highly effective catalyst for a broad range of alkyne metathesis reactions.
- The catalyst's ability to activate terminal alkynes expands its synthetic utility.
- These findings contribute to the development of advanced catalytic systems for alkyne transformations.
Related Concept Videos
Preparation of Alkynes: Alkylation Reaction
Alkylation of terminal alkynes with primary alkyl halides in the presence of a strong base like sodium amide is one of the common methods for the synthesis of longer carbon-chain alkynes. For example, treatment of 1-propyne with sodium amide followed by reaction with ethyl bromide yields 2-pentyne.
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
Alkynes to Aldehydes and Ketones: Acid-Catalyzed Hydration
Analogous to alkenes, alkynes also undergo acid-catalyzed hydration. While the addition of water to an alkene gives an alcohol, hydration of alkynes produces different products such as aldehydes and ketones.
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
Preparation of Alkynes: Dehydrohalogenation
Alkynes can be prepared by dehydrohalogenation of vicinal or geminal dihalides in the presence of a strong base like sodium amide in liquid ammonia. The reaction proceeds with the loss of two equivalents of hydrogen halide (HX) via two successive E2 elimination reactions.
Acidity of 1-Alkynes
The acidic strength of hydrocarbons follows the order: Alkynes > Alkenes > Alkanes. The strength of an acid is commonly expressed in units of pKa — the lower the pKa, the stronger the acid. Among the hydrocarbons, terminal alkynes have lower pKa values and are, therefore, more acidic. For example, the pKa values for ethane, ethene, and acetylene are 51, 44, and 25, respectively, as shown here.
