Solmaz KARABULUT, Bengi Özgün ÖZTÜRK, Yavuz İMAMOĞLU

O-içeren Norbornen Türevlerinin Rutenyum- başlatıcı ile Halka Açılımı Metatez Polimerizasyonu

B u çalışmada, monometalik rutenyum alkiliden kompleksleri kullanılarak homobimetalik rutenyum kompleksleri sentezlendi. Ligandlardaki monometalik kısımlar fosfin, N-heterosiklik karben ve Schiff Bazı ligandları ile değiştirildi. Homometalik komplekslerin oluşumuna ligandın etkisi ve bunların ROMP Halka Açılımı Metatez Polimerizasyonu aktiviteleri araştırıldı. Sentezlenen kompleksler ve polimerler 1H-NMR ve FTIR teknikleri ile tanımlandı ve aktivite sonuçları monometalik türlerle karşılaştırıldı

Anahtar Kelimeler:

O-içeren norbornen türevleri, Olefin metatez, Rutenyum alkiliden, Organometalilk katalizör, ROMP

Ruthenium-initated Ring Opening Metathesis Polymerization of O-containing Norbornene Derivatives

In this study, several homobimetallic ruthenium complexes were synthesized by using monometallic ruthenium alkylidene complexes. The ligands in monometallic fractions were modified by phosphine, N-heterocyclic carbene and Schiff Base ligands. The effect of the ligands on formation of homobimetallic complexes and their ROMP Ring Opening Metathesis Polymerization activity were investigated. The synthesized complexes and ROMP polymers were characterized by 1H-NMR and FT-IR and the activity results were compared with corresponding monometallic analogs.

Keywords:

O-containing norbornene derivatives, Olefin metathesis, Ruthenium alkylidene, Organometallic catalyst, ROMP,

PDF

___

1. NG. Gaylord, BM. Mandal, M. Martan, Peroxideinduced polymerization of norbornene, J. Polym. Sci. Pol. Lett. Ed., 14 (1976) 555.
2. BL. Goodall, H. McIntosh, LF. Rhodes, New Catalysts for the Polymerizatıon of Cyclic Olefins Macromol. Symp., 89 (1995) 421.
3. TFA. Haselwander, W. Heitz, SA. Krugel, JH. Wendorff, Polynorbornene: synthesis, properties and simulations, Macromol. Chem. Phys., 197 (1996) 3435.
4. JC. Mol, Industrial applications of olefin metathesis, J. Mol. Catal. A: Chem., 213 (2004) 39.
5. JC. Mol, Industrial applications of olefin metathesis, In Novel Metathesis Chemistry Designing WellDefined Initiator Systems for Specialty Chemical Synthesis, Tailored Polymers and Advanced Materials Applications, İmamoğlu Y, Bencze L. (eds.)., NATO ASI Series V122., Kluwer Academic Publishers: Dordrecht, (2003) 313.
6. RH. Grubbs, Handbook of Metathesis, Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim, Germany, 3 (2003) 413.
7. KJ. Ivin, JC. Mol, Olefin Metathesis and Metathesis Polymerization, Academic Press, Inc., London, 1997, 302.
8. MR. Buchmeiser, Homogeneous Metathesis, Polymerization by Well-Defined Group VI and Group VIII Transition-Metal Alkylidenes: Fundamentals and Applications in the Preparation of Advanced Materials Chem. Rev., 100 (2000) 1565.
9. E. Khosravi, T. Szymanska-Buzar, Ring Opening Metathesis Polymerization and Related Chemistry, Kluwer Academic Publishers, The Netherlands, 2002, 91.
10. ESh. Finkelshtein, KL. Makovetskii, YuP. Yampolskii, EB. Portnykh, IYa. Ostrovskaya, NE. Kaliuzhnyi, NA. Pritula, AI. Golberg, MS. Yatsenko, NA. Plate, Makromol. Chem., 192 (1991) 1.
11. ESh. Finkelshtein, EB. Portnykh, KL. Makovetskii, IYa. Ostrovskaya, NB. Bespalova, YuP. Yampolskii, In Metathesis Polymerization of Olefins and Polymerization of Alkynes, Imamoglu, Y., Ed., NATO ASI Series C 506, Kluwer: Dordrecht, The Netherlands, (1998) 189.
12. Y. Kawakami, H. Toda, M. Higashino, Y. Yamashita, Polynorbornene with Oligodimethylsiloxanyl Substituents for Selectively Oxygen Permeable Membrane Material, Polym. J., 20 (1988) 285.
13. RR. Schrock, High Oxidation State Multiple MetalCarbon Bonds, Chem. Rev., 102 (2002) 145.
14. RR. Schrock, The Discovery and Development of High-Oxidation State Mo and W Imido Alkylidene Complexes for Alkene Metathesis, In Handbook of Metathesis; Grubbs, R. H., Ed.; Wiley-VCH: Weinheim, Germany, 1 (2004) 8.
15. RR. Schrock, High Oxidation State Alkylidene and Alkylidyne Complexes, Chem. Commun., 2005 (2004) 2773.
16. RH. Grubbs, Handbook of Metathesis, 1st ed., Grubbs, R. H., Ed., Wiley-VCH: Weinheim, Germany, 2003; Vol. 1-3.
17. TM. Trnka, RH. Grubbs, The Development of L2X2Ru= CHR Olefin Metathesis Catalysts: An Organometallic Success Story, Acc. Chem. Res., 34 (2001) 18.
18. KJ. Ivin, AM. Kenwright, E. Khosravi, JG. Hamilton, Ring-Opening Metathesis Polymerization of 7-tertButoxybicyclo [2.2.1]hepta-2,5-diene Initiated by Well-Defined Molybdenum and Ruthenium Carbene Complexes, Macromol. Chem. Phys., 202 (2001) 3624.
19. DM. Haigh, AM. Kenwright, E. Khosravi, RingOpening Metathesis Polymerisations of 7-tertButoxynorbornadiene and its Derivatives: A Study on the Regeneration of Grubbs Catalyst, Tetrahedron, 60 (2004) 7217.
20. DM. Haigh, AM. Kenwright, Nature of the Propagating Species in Ring-Opening Metathesis Polymerizations of Oxygen-Containing Monomers Using Well-Defined Ruthenium Initiators, E. Khosravi, Macro-molecules, 38 (2005) 7571.
21. S. Çetinkaya, S. Karabulut, Y. İmamoğlu, Metathesis copolymerization of 1,5-cyclooctadiene and norbornene with electrochemically generated WCl6-based active species Eur. Polym. J., 41 (2005) 467.
22. S. Karabulut, S. Çetinkaya, B. Düz, Y. İmamoğlu, Ring-opening metathesis polymerization of cyclododecene using an electrochemically reduced tungsten-based catalyst, Appl. Organometal. Chem., 18 (2004) 375.
23. S. Karabulut, S. Çetinkaya, B. Düz, Y. İmamoğlu, Electrochemically reduced tungsten-based active species as catalysts for metathesis-related reactions: Ring opening metathesis copolymerization of cyclopentene with cyclooctene, Appl. Organometal. Chem., 19 (2005) 997.
24. S. Çetinkaya, S. Karabulut, B. Düz, Y. İmamoğlu, Synthesis and characterization of polyoctenamer with WCl6-e-Al-CH2Cl2 catalyst system via ring opening metathesis polymerization Appl. Organometal. Chem., 19 (2005) 347.
25. O. Dereli, B. Düz, BK. Zümreoğlu, Y. İmamoğlu, Electrochemically generated tungsten-based active species as catalysts for metathesis-related reactions: 2. Ring-opening metathesis polymerization of norbornene, Appl. Organometal. Chem., 18 (2004) 130.
26. S. Karabulut, C. Aydogdu, B. Düz, Y. İmamoğlu, Metal-Containing Polymers Synthesized via Acyclic Diene Metathesis (ADMET) Polymerization Using Electrochemically Reduced TungstenBased Catalyst: Polycarbogermanes, J. Inorg. & Organometal. Pol. and Mat., 16 (2006) 115.
27. S. Karabulut, C. Aydogdu, B. Düz, Y. İmamoğlu, Synthesis and characterization of Ge- and Sncontaining ADMET polymers, J. Mol. Catal., 254 (2006) 186.
28. S. Karabulut, C. Aydogdu, B. Düz, Y. İmamoğlu, Metal-Containing Polymers Synthesized via Acyclic Diene Metathesis (ADMET) Polymerization Using Electrochemically Reduced Tungsten-Based Catalyst: Polycarbosilanes, J. Inorg. & Organometal. Pol. and Mat., 17 (2007) 517.
29. O. Dereli, C. Aydogdu, B. Düz, Y. İmamoğlu, Application of electrochemically generated molybdenum-based catalyst system to the ring-opening metathesis polymerization of norbornene and a comparison with the tungsten analogue, Appl. Organometal. Chem., 19 (2005) 834.
30. EL. Dias, RH. Grubbs, Synthesis and Investigation of Homo- and Heterobimetallic Ruthenium Olefin Metathesis Catalysts Exhibiting Increased Activities, Organometallics 17 (1998) 2758.
31. W. Baratta, WA. Herrmann, P. Rigo, J. Schwarz, Convenient syntheses of novel ruthenium catalysts bearing N-heterocyclic carbenes, J. Organomet. Chem., 593 (2000) 489.
32. AJ. Arduengo, R. Krafczyk, R. Schmutzler, Imidazolylidenes, imidazolinylidenes and imidazolidines, Tetra-hedron 55 (1999) 14523.
33. A. Fürstner, L. Ackermann, B. Gabor, R. Goddard, CW. Lehmann, R. Mynott, Comparative Investigation of Ruthenium-Based Metathesis Catalysts Bearing N-Heterocyclic Carbene (NHC) Ligands, Chem. Eur. J., 7 (2001) 3236.