6533b82ffe1ef96bd1295d7c
RESEARCH PRODUCT
Reactions of Alkenes and Alkynes with an Acyclic Silylene and Heavier Tetrylenes under Ambient Conditions
Philip P. PowerHeikki M. TuononenAkseli MansikkamäkiFelicitas LipsJames C. Fettingersubject
DieneTrimethylsilylacyclic silyleneAlkynealkeenit ja alkyynitPhotochemistryMedicinal chemistryInorganic Chemistrychemistry.chemical_compoundraskaammat tetryleenitalkenes and alkynesCyclopenteneambient conditionssykloadditioreaktiotPhysical and Theoretical Chemistryasyklinen silyleeniDiphenylacetyleneta116chemistry.chemical_classificationOrganic ChemistrySilylenecyloaddition reactionsCycloadditionPhenylacetylenechemistrynormaalit ympäristön olosuhteethevier tetrylenesdescription
Cycloaddition reactions of the acyclic silylene Si(SAriPr4)2 (AriPr4 = C6H3-2,6(C6H3-2,6-iPr2)2) with a variety of alkenes and alkynes were investigated. Its reactions with the alkynes phenylacetylene and diphenylacetylene and the diene 2,3-dimethyl-1,3-butadiene yielded silacycles (AriPr4S)2tiebar above startSi(CH═tiebar above endCPh) (1), (AriPr4S)2tiebar above startSi(PhC═tiebar above endCPh) (2), and (AriPr4S)2tiebar above startSiCH2CMeCMetiebar above endCH2 (3) at ambient temperature. The compounds were characterized by X-ray crystallography, 1H, 13C, and 29Si NMR spectroscopy, and IR spectroscopy. No reaction was observed with more substituted alkenes such as propene, (Z)-2-butene, tert-butylethylene, cyclopentene, 1-hexene, or the alkyne bis(trimethylsilyl)acetylene under the same reaction conditions. The germylene Ge(SArMe6)2 and stannylene Sn(SArMe6)2 (ArMe6 = C6H3-2,6(C6H2-2,4,6-Me3)2) analogues of Si(SArMe6)2 displayed no reaction with ethylene. Quantum chemical calculations using model tetrylenes E(SPh)2 (E = Si, Ge, Sn; Ph = C6H5) show that cyclization reactions are endothermic in the case of germanium and tin derivatives but energetically favored for the silicon species. peerReviewed
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2014-10-09 |