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Chemical Precipitation Method for the Synthesis of Nb2O5 Modified Bulk Nickel Catalysts with High Specific Surface Area
Published on: February 19, 2018
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Development of Nickel Hydrosilylation Catalysts
Yumiko Nakajima1, Kazuhiko Sato2, Shigeru Shimada3
1Interdisciplinary Research Center for Catalytic Chemistry, National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba Central 51-1-1 Higashi, Tsukuba, Ibaraki, 305-8565, Japan. yumiko-nakajima@aist.go.jp.
Chemical Record (New York, N.Y.)
|August 9, 2016
Summary
Nickel catalysts efficiently perform alkene hydrosilylation under mild conditions. Novel mechanisms involving allyl ligands facilitate silicon-hydrogen bond activation and silicon-carbon bond formation for versatile applications.
Area of Science:
- Organometallic Chemistry
- Catalysis
- Organic Synthesis
Background:
- Hydrosilylation is a key reaction in organic synthesis for forming carbon-silicon bonds.
- Nickel catalysis offers a cost-effective alternative to precious metal catalysts.
- Developing efficient and selective nickel catalysts for hydrosilylation remains an active research area.
Purpose of the Study:
- To describe studies on nickel-catalyzed hydrosilylation reactions.
- To investigate the catalytic activity of various nickel complexes, including (salicylaldiminato)methylnickel and Ni(II) salts.
- To explore the mechanism of nickel-catalyzed hydrosilylation.
Main Methods:
- Synthesis and application of (salicylaldiminato)methylnickel complexes.
- Utilizing commercially available Ni(II) salts as catalyst precursors with NaBHEt3.
- Employing arene-supported cationic nickel allyl complexes.
- Performing mechanistic studies using experimental data and Density Functional Theory (DFT) calculations.
Main Results:
- Efficient catalysis of alkene hydrosilylation using (salicylaldiminato)methylnickel complexes under ambient conditions.
- Versatile catalytic activity of Ni(II) salts and their derivatives in the presence of NaBHEt3.
- Successful hydrosilylation of industrially relevant alkenes (siloxy-, amino-, epoxy-substituted).
- High selectivity observed with secondary hydrosilanes.
- Identification of a novel catalytic mechanism involving facile Si-H bond cleavage and Si-C bond formation, aided by the allyl ligand.
Conclusions:
- Nickel complexes, including (salicylaldiminato)methylnickel and Ni(II) systems, are effective catalysts for alkene hydrosilylation.
- The developed catalytic systems demonstrate broad substrate scope and high selectivity.
- A novel mechanism elucidates the catalytic cycle, highlighting the cooperative role of the allyl ligand.
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