153814-39-2Relevant articles and documents
Novel Catalytic Metathesis of Substituted Olefins Promoted by Rhenium(I) Enolate Complexes
Hirano, Masafumi,Hirai, Miwa,Ito, Yuji,Fukuoka, Atsushi,Komiya, Sanshiro
, p. 165 - 166 (1994)
Rhenium(I) enolate complexes Re(NCCHCO2Et)(PMe2Ph)4 and Re(NCCHCO2Et)(NCCH2CO2Et)(PMe2Ph)4 are found to catalyze unique olefin metathesis reaction of tetracyanoethylene with ethyl α-cyanocinnamate to give 1,1-dicyano-2-phenylethylene and ethyl 2,3,3-tricyanopropenoate at room temperature.
Room temperature dynamic polymers based on Diels-Alder chemistry
Reutenauer,Buhler,Boul,Candau,Lehn
experimental part, p. 1893 - 1900 (2009/09/28)
Dynamers based on reversible Diels-Alder chemistry have been obtained and shown to undergo dynamic exchange at room temperature. Their study in solution by small-angle neutron scattering indicated the formation of long and highly flexible chains. Polydispersed molecules gave Tg values below room temperature, permitting the generation of a dynamic elastomer upon introduction of a dynamic cross-linking agent. The use of a system with a low equilibrium constant gives access to materials with interesting self-healing properties.
N-bonded enolatorhenium(I) complexes having dimethylphenylphosphine ligands as active key intermediates in catalytic Knoevenagel and Michael reactions
Hirano, Masafumi,Hirai, Miwa,Ito, Yuji,Tsurumaki, Tsutomu,Baba, Atsushi,Fukuoka, Atsushi,Komiya, Sanshiro
, p. 3 - 14 (2007/10/03)
Enolatorhenium(I) complexes cis-Re(NCCRCO2R′)(NCCHRCO2R′)(PMe 2Ph)4 (R=H, R′=Me (2a); R=H, R′=Et (2b); R=H, R′=n-Bu (2c); R=Me, R′=Et (2d)) are prepared by the reaction of ReH(N2)(PMe2Ph)4 (1) with alkyl cyanoalkyl carboxylate. X-ray structure analysis of 2b shows that it has an octahedral Re geometry, where mutually cis enolato and ester ligands bind to the rhenium via cyano groups. Reaction of 2b with benzaldehyde gives Re(NCCHCO2Et)[NC(EtO2C)C=CHPh]-(PMe2Ph) 4 (4), which is also derived from the ligand exchange reaction of 2b with ethyl (E)-2-cyano-3-phenylpropenoate. These rhenium(I) complexes 1, 2, and 4 catalyze Knoevenagel and Michael reactions under neutral and mild conditions. A possible mechanism for the Knoevenagel reaction has been proposed.
Synthesis and Electrochemical Properties of 4-Phenyl-1-buten-3-yne-1,1,2-tricarbonitriles and Tricyanoacrylates
Dulog, Lothar,Koerner, Bernd,Heinze, Juergen,Yang, Jianjun
, p. 1663 - 1672 (2007/10/02)
The reaction of phenylacetylenes 4a-h copper(I) acetate (5) and TCNE (tetracyanoethylene) in THF/acetonitrile gave 4-phenyl-1-buten-3-yne-1,1,2-tricarbonitriles 6a-h. 4i did not react to give 6i.The phenylacetylenes 4b-i were prepared by a two-step synthesis starting from the corresponding phenyl halides 1b-i.The tricyanoacrylates 8 were synthesised from the corresponding cyanoacetates 7, TCNE and catalytic amounts of pyridine in THF. - Cyclovoltammetric investigations showed that the butenynes 6 and the tricyanoacrylates 8 are strong electron acceptors which can be easily reduced.The radical anions 6.- are unstable in acetonitrile and react irreversibly with 6 to give oligomeric anions 6.-n.Only 4-(2,4,6-trimethoxyphenyl)-1-buten-3-yne-1,1,2-tricarbonitrile (6h) is reduced to a radical anion 6h.- which associates with 6h in a reversible follow-up process to form a dimeric anion 6h2.-.By contrast, the tricyanoacrylates 8 can be reversibly reduced to their respective radical anions and dianions. - Keywords: Cyano compounds, conjugated / Phenylacetylenes / Radical anions / Electrochemistry
