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Investigation and Study of Monomers and Polymers Based on Known Metal Induced Couplings of Alkynes and Diynes Jesse Quinn Ryerson University

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Investigation and Study of Monomers and Polymers Based on Known Metal Induced Couplings of Alkynes and Diynes Jesse Quinn Ryerson University Ryerson University Digital Commons @ Ryerson Theses and dissertations 1-1-2013 Investigation And Study Of Monomers And Polymers Based On Known Metal Induced Couplings Of Alkynes And Diynes Jesse Quinn Ryerson University Follow this and additional works at: http://digitalcommons.ryerson.ca/dissertations Part of the Biochemistry, Biophysics, and Structural Biology Commons Recommended Citation Quinn, Jesse, "Investigation And Study Of Monomers And Polymers Based On Known Metal Induced Couplings Of Alkynes And Diynes" (2013). Theses and dissertations. Paper 2019. This Thesis is brought to you for free and open access by Digital Commons @ Ryerson. It has been accepted for inclusion in Theses and dissertations by an authorized administrator of Digital Commons @ Ryerson. For more information, please contact [email protected]. INVESTIGATION AND STUDY OF MONOMERS AND POLYMERS BASED ON KNOWN METAL INDUCED COUPLINGS OF ALKYNES AND DIYNES by Jesse Quinn B.Sc., Ryerson University, 2010 A thesis presented to Ryerson University in partial fulfillment of the requirements for the degree of Master of Science in the program of Molecular Science Toronto, Ontario, Canada, 2013 © Jesse Quinn 2013 Author’s Declaration I hereby declare that I am the sole author of this thesis. This is a true copy of the thesis, including any required final revisions, as accepted by my examiners. I authorize Ryerson University to lend this thesis to other institutions or individuals for the purpose of scholarly research. I further authorize Ryerson University to reproduce this thesis by photocopying or by other means, in total or in part, at the request of other institutions or individuals for the purpose of scholarly research. I understand that my thesis may be made electronically available to the public. ii INVESTIGATION AND STUDY OF MONOMERS AND POLYMERS BASED ON KNOWN METAL INDUCED COUPLINGS OF ALKYNES AND DIYNES Jesse Quinn Master of Science, Molecular Science, Ryerson University 2013 Abstract Both reduced zirconocene ("Cp2Zr") and zero valent lithium are known to induce coupling of alkynes to form dimers, oligmers, and polymers. Established work from Fagan et al., Tilley et al., and Eisch et al. was used as the basis for the synthesis of desired targets. First, the attempted syntheses of novel Group IV metalloles from a zirconocene intermediate were studied. There was no conclusive data to state that 2,3,4,5-tetraphenylzirconacyclopentadiene will undergo metallacycle transfer with CrCl3 and FeCl3. The presence of zirconocene dichloride suggests that metallacycle transfer may have occurred, which warrants further investigation. Monomers, 1-bromo-4-hex-1-ynyl-benzene, 1-bromo-3-(phenylethynyl)benzene, and p-dihex-1-ynylbenzene, were synthesized successfully via Sonogashira coupling. Attempts to 1 synthesize novel monomers via lithium and "Cp2Zr" had mixed results. H NMR acquisition of the hydrolyzed product from zirconocene-coupling of 1-bromo-3-(phenylethynyl)benzene appeared to be successful. Lastly, lithium and "Cp2Zr" induced polymerization of novel monomers and known monomers were attempted. Metallacycle transfer from the zirconocene intermediate polymers to thiophene, thiopheneoxide, thiophenedioxide, and phosphole were attempted. However, limited characterization was completed. 1H NMR acquisitions suggest polymer by the loss of resolution and broadening of resonance signals, but further characterization via GPC is required. Monomers, and polymers were characterized using various means such as 1H, 13C, 31P, 119Sn NMR spectroscopy, UV-Vis spectroscopy, AIMS AccuTOF-DART mass spectrometry and GPC. iii Acknowledgements First and foremost I would like to express my sincere gratitude to Dr. McWilliams and Dr. McCarthy. I want to thank them for this research opportunity, support, and their guidance along the way. I would also like to thank Dr. Foucher, and Dr. Wylie for their support and guidance. I would also like to especially thank Dr. Viirre for valuable support and guidance. Moreover, it was a pleasure to have met and worked with each and one of his students. I would also like to thank my fellow lab mate Jennifer Nguyen. She was an excellent student to have guided and I wish her all the best in future endeavours. I would also like to thank the Dr. Viirre lab members, Bashar Alkhouri, Salma Elmallah, Rob Denning, and Vassilios Kanellis for support and much needed education on all things organic. Lastly, I would like to thank my girlfriend, Stephanie Ruediger, and my father, Paul Quinn, for their support when I was stressed. iv Table of Contents Author’s Declaration .................................................................................................................................. ii Abstract ....................................................................................................................................................... iii Acknowledgements ..................................................................................................................................... iv Table of Contents ........................................................................................................................................ v List of Tables .............................................................................................................................................. ix List of Schemes ............................................................................................................................................ x List of Figures ............................................................................................................................................ xii List of Abbreviations ................................................................................................................................ xiv 1 Introduction ........................................................................................................................................... 1 1.1 Electrophilic substitution (metallacycle transfer) ....................................................................... 2 1.1.1 A brief discussion of zirconium metallacycles and similar metallacycles ............................... 3 1.1.1.1 Zirconocene-coupling stability, mechanism, and reversibility of such couplings ............. 4 1.1.1.2 Alternative metallocyclopentadienes for stoichiometric or catalytic cycloaddition reactions and other organic reactions ................................................................................................ 8 1.1.2 Lithium metal dimerized diarylacetylene ................................................................................. 9 1.1.3 Stannoles ................................................................................................................................. 12 1.1.4 A brief discussion of other heteroles ...................................................................................... 13 1.2 A brief history of Sonogashira coupling .................................................................................... 14 1.3 A brief discussion of project relevant polymers ........................................................................ 16 1.3.1 Dimerization and polymerization via nickel metal complexes ............................................... 16 1.3.2 Zirconocene-Coupling of Diynes ............................................................................................ 24 1.4 An introduction to macrocycles .................................................................................................. 26 1.4.1 Zirconocene-Coupling Reversibility Related to Macrocyclization ........................................ 28 1.4.2 Zirconacyclopentadiene macrocycle and post modifications ................................................. 30 1.5 Optical properties of poly(phenylenedieneylene)s .................................................................... 31 1.6 Aim of Project .............................................................................................................................. 32 2 Results and discussion ........................................................................................................................ 33 2.1 Synthesis of metallole precursors and attempts at synthesis of metalloles ............................. 33 2.1.1 Synthesis of 2,3,4,5-tetraphenylzirconacyclopentadiene (3) and derivatives (102 to 104) ..... 34 2.1.1.1 Characterization of compound 3 and derivatives (102 to 104) ........................................ 36 v 2.1.1.2 Characterization of the brown oil from the attempted synthesis of 103 .......................... 40 2.1.1.3 Characterization of the crystals isolated from the attempted synthesis of 104 ................ 41 2.1.2 Synthesis of 1,4-dilthio-1,2,3,4-tetraphenyl-1,3-butadiene (8) and derivatives (9, and 102) . 42 2.1.2.1 Characterization of compound 8 and derivatives (9, and 102) ........................................ 43 2.2 Synthesis of monomers via Castro-Stephens and Sonogashira coupling ................................ 47 2.2.1 Synthesis of compounds 106, 107, 111, and 113 .................................................................... 47 2.2.1.1 Characterization of compounds 106, 107, 111, and 113 ................................................. 48 2.3 Attempted synthesis of novel monomers using 1-bromo-3-(phenylethynyl)benzene (111) as starting material for zero valent nickel polymerization ...................................................................
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