Synthesis and X-ray Crystallographic Studies of Diacetylenic Molecules Bearing Triorganosilyl, Triorganostannyl, and Diorganophosphanyl Substituents. Investigation of Their Solid-State and Molten-Stat

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• 作者：Francis Carré ; Nathalie Devylder ; Sylvain G. Dutremez ; Christian Gué ; rin ; Bernard J. L. Henner ; Agn&egrave ; s Jolivet ; Vé ; ronique Tomberli ; and Franç ; oise Dahan
• 刊名：Organometallics
• 出版年：2003
• 出版时间：May 12, 2003
• 年：2003
• 卷：22
• 期：10
• 页码：2014 - 2033
• 全文大小：435K
• 年卷期：v.22,no.10(May 12, 2003)
• ISSN：1520-6041

文摘

The following series of silicon-containing diacetylenes has been prepared: R₃SiCges/entities/tbd1.gif">CCges/entities/tbd1.gif">CSiR₃ (R₃ = Me₃ (2a); R₃ = Me₂Ph (2b); R₃ = MePh₂ (2c); R₃ = Ph₃ (2d)), rac-MePhNpSiCges/entities/tbd1.gif">CCges/entities/tbd1.gif">CSiMePhNp (2e: Np = 1-naphthyl), (R,R)-(+)-MePhNpSiCges/entities/tbd1.gif">CCges/entities/tbd1.gif">CSiMePhNp (2e*),rac-Ph₃SiCges/entities/tbd1.gif">CCges/entities/tbd1.gif">CSiMePhNp (3), (R)-(+)-Ph₃SiCges/entities/tbd1.gif">CCges/entities/tbd1.gif">CSiMePhNp (3*), R₃SiCH₂Cges/entities/tbd1.gif">CCges/entities/tbd1.gif">CCH₂SiR₃ (R₃ = Me₃ (4a); R₃ = Ph₃ (4b)), R₂HSiCges/entities/tbd1.gif">CCges/entities/tbd1.gif">CSiHR₂ (R₂ = Me₂ (5a); R₂ = Ph₂(5b)), R₃SiCges/entities/tbd1.gif">CCges/entities/tbd1.gif">CH (R₃ = Me₃ (6a); R₃ = Ph₃ (6b)), and rac-MePhNpSiCges/entities/tbd1.gif">CCges/entities/tbd1.gif">CH (6c).Single-crystal X-ray diffraction analyses were performed on 2a, 2d, 2e*, 4a, and 4b todetermine the R_1,4 distance and the angle ges/gifchars/gamma.gif" BORDER=0 > between neighboring diacetylenic rods in thesolid. Diacetylenes 2a, 2e*, and 4a were tested for ges/gifchars/gamma.gif" BORDER=0 >-ray and heat-induced solid-statepolymerization reactivity, and in accordance with the X-ray results, polymerization was notobserved. Terminal diyne 6c showed no polymerization activity upon irradiation with a 100krad dose of ges/gifchars/gamma.gif" BORDER=0 >-rays but slowly polymerized in the solid state when heated to 70 ges/entities/deg.gif">C for 13days. Following a preliminary investigation of 2a, 2d, 2e, 2e*, 3*, 4a, 4b, 5a, 5b, 6a, 6b,and 6c by differential scanning calorimetry (DSC), these diynes were polymerized in themolten state or just below melting. MALDI-TOF mass spectrometry shows that the polymersconsist of mixtures of oligomers with 2 to 10 repeat units. The constituting motif of theseoligomers (enyne, butatriene, polyaromatic) was elucidated by use of infrared and solutionand solid-state multinuclear NMR spectroscopies. Polymerization experiments were alsocarried out on Me₃SnCges/entities/tbd1.gif">CCges/entities/tbd1.gif">CSnMe₃ (7a), Ph₃SnCges/entities/tbd1.gif">CCges/entities/tbd1.gif">CSnPh₃ (7b), and Ph₂PCges/entities/tbd1.gif">CCges/entities/tbd1.gif">CPPh₂ (8), and the results of these experiments are compared with the polymerization resultsof their silicon-containing analogues. A 1,4-addition process takes place with 2a, 2d, 2e,2e*, 3*, 5a, 5b, 7a, 7b, and 8, leading to butatriene and/or enyne structures. A 1,2-additionprocess is operative in the case of monosilylated derivatives 6a, 6b, and 6c, giving acetylenicpolyenes. Molten-state polymerization of 4a and 4b gives polyaromatic structures.