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 ; Agnè ; 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: R3SiC
CCCSiR3 (R3 = Me3 (2a); R3 = Me2Ph (2b); R3 = MePh2 (2c); R3 = Ph3 (2d)), rac-MePhNpSiCCCCSiMePhNp (2e: Np = 1-naphthyl), (R,R)-(+)-MePhNpSiCCCCSiMePhNp (2e*),rac-Ph3SiCCCCSiMePhNp (3), (R)-(+)-Ph3SiCCCCSiMePhNp (3*), R3SiCH2CCCCCH2SiR3 (R3 = Me3 (4a); R3 = Ph3 (4b)), R2HSiCCCCSiHR2 (R2 = Me2 (5a); R2 = Ph2(5b)), R3SiCCCCH (R3 = Me3 (6a); R3 = Ph3 (6b)), and rac-MePhNpSiCCCCH (6c).Single-crystal X-ray diffraction analyses were performed on 2a, 2d, 2e*, 4a, and 4b todetermine the R1,4 distance and the angle 
between neighboring diacetylenic rods in thesolid. Diacetylenes 2a, 2e*, and 4a were tested for -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 -rays but slowly polymerized in the solid state when heated to 70 
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 Me3SnCCCCSnMe3 (7a), Ph3SnCCCCSnPh3 (7b), and Ph2PCCCCPPh2 (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.
CCCSiR3 (R3 = Me3 (2a); R3 = Me2Ph (2b); R3 = MePh2 (2c); R3 = Ph3 (2d)), rac-MePhNpSiCCCCSiMePhNp (2e: Np = 1-naphthyl), (R,R)-(+)-MePhNpSiCCCCSiMePhNp (2e*),rac-Ph3SiCCCCSiMePhNp (3), (R)-(+)-Ph3SiCCCCSiMePhNp (3*), R3SiCH2CCCCCH2SiR3 (R3 = Me3 (4a); R3 = Ph3 (4b)), R2HSiCCCCSiHR2 (R2 = Me2 (5a); R2 = Ph2(5b)), R3SiCCCCH (R3 = Me3 (6a); R3 = Ph3 (6b)), and rac-MePhNpSiCCCCH (6c).Single-crystal X-ray diffraction analyses were performed on 2a, 2d, 2e*, 4a, and 4b todetermine the R1,4 distance and the angle between neighboring diacetylenic rods in thesolid. Diacetylenes 2a, 2e*, and 4a were tested for -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 -rays but slowly polymerized in the solid state when heated to 70 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 Me3SnCCCCSnMe3 (7a), Ph3SnCCCCSnPh3 (7b), and Ph2PCCCCPPh2 (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.