Insight into the Thermal Ring-Opening Polymerization of Phospha[1]ferrocenophanes.
作者： Elaheh Khozeimeh Sarbisheh , Jose Esteban Flores , Jianfeng Zhu , Jens Müller
关键词:
摘要: A mixture of cis/trans isomers phospha[1]ferrocenophanes equipped with one iPr group at the α position to bridging PhP moiety was prepared. Both (cis-4 and trans-4) were obtained as racemates could be separated so that their thermal properties investigated individually. The molecular structure cis-4 determined by single-crystal X-ray analysis showing a tilt angle α=26.35(8)°. Interconversion between both occurred in melt elevated temperatures revealed trans isomer is thermodynamically more stable. Structural thermodynamic data complemented DFT calculations (B3PW91/6-311+G(d,p) B3PW91-D3(BJ)/6-311+G(d,p)). Performance ring-opening polymerization (ROP) trans-4 230 °C gave polymers cyclic oligomers. Gel permeation chromatography (GPC) sulfurized polymer resulted weight 62.5 kDa (Mw) polydispersity index 1.39 (PDI). Mass spectrometric oligomers showed presence species from dimers heptamers. After sulfurization, preparative thin layer led separation three isomeric dimers. characterization these conclusion Fe−Cp bond breaks during ROP process. mechanism similar known photolytic ferrocenophanes proposed.
sci-hub.se 参考文章(97)
Lan Cao, Mitchell A. Winnik, Ian Manners, Anionic Ring-Opening Polymerization (ROP) of a Phosphorus-Bridged [1]Ferrocenophane Initiated by Living Polystyrene and Polyisoprene: Synthesis of Novel Organic–Poly(ferrocenylphosphine) Block Copolymers Journal of Inorganic and Organometallic Polymers and Materials. ,vol. 8, pp. 215- 224 ,(1998) , 10.1023/A:1021484010088
Kieron Burke, John P. Perdew, Yue Wang, Derivation of a generalized gradient approximation: The PW91 density functional Springer, Boston, MA. pp. 81- 111 ,(1998) , 10.1007/978-1-4899-0316-7_7
Il Nam Jung, Paul Ronald Jones, Hyperconjugative vs. d orbital effects in unsaturated silanes Journal of Organometallic Chemistry. ,vol. 101, pp. 27- 34 ,(1975) , 10.1016/S0022-328X(00)88529-0
Chantal Paquet, Paul W. Cyr, Eugenia Kumacheva, Ian Manners, Polyferrocenes: metallopolymers with tunable and high refractive indices Chemical Communications. pp. 234- 235 ,(2004) , 10.1039/B311934C
Ian R. Butler, Mixed phosphino-bipyridylferrocenes Polyhedron. ,vol. 11, pp. 3117- 3121 ,(1992) , 10.1016/S0277-5387(00)83651-7
William F. Bailey, Mark R. Luderer, Kevin P. Jordan, Effect of solvent on the lithium-bromine exchange of aryl bromides : Reactions of n-butyllithium and tert-butyllithium with 1-bromo-4-tert-butylbenzene at 0 °C Journal of Organic Chemistry. ,vol. 71, pp. 2825- 2828 ,(2006) , 10.1021/JO060026U
John K. Pudelski, Daniel A. Foucher, Charles H. Honeyman, Peter M. Macdonald, Ian Manners, Stephen Barlow, Dermot O'Hare, Synthesis, Characterization, and Properties of High Molecular Weight Poly(methylated ferrocenylsilanes) and Their Charge Transfer Polymer Salts with Tetracyanoethylene Macromolecules. ,vol. 29, pp. 1894- 1903 ,(1996) , 10.1021/MA9511863
Xiangdong Feng, Benoît Pugin, Ernst Küsters, Gottfried Sedelmeier, Hans-Ulrich Blaser, Josiphos Ligands with an Imidazolium Tag and their Application for the Enantioselective Hydrogenation in Ionic Liquids Advanced Synthesis & Catalysis. ,vol. 349, pp. 1803- 1807 ,(2007) , 10.1002/ADSC.200600636
Daniel A. Foucher, Ben Zhong Tang, Ian Manners, Ring-opening polymerization of strained, ring-tilted ferrocenophanes: a route to high-molecular-weight poly(ferrocenylsilanes) Journal of the American Chemical Society. ,vol. 114, pp. 6246- 6248 ,(1992) , 10.1021/JA00041A053
Chantal Paquet, Paul W. Cyr, Eugenia Kumacheva, Ian Manners, Rationalized Approach to Molecular Tailoring of Polymetallocenes with Predictable Optical Properties Chemistry of Materials. ,vol. 16, pp. 5205- 5211 ,(2004) , 10.1021/CM049403E