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Stereospecific Styrene Enchainment at a Titanium Site within a Helical Ligand Framework: Evidence for the Formation of Homochiral Polystyrene

2007; Wiley; Volume: 46; Issue: 25 Linguagem: Inglês

10.1002/anie.200700783

ISSN

1521-3773

Autores

Klaus Beckerle, Ramanujachary Manivannan, Bing Lian, Geert‐Jan M. Meppelder, Gerhard Raabe, Thomas P. Spaniol, Henner Ebeling, Frédéric Pelascini, Rolf Mülhaupt, Jun Okuda,

Tópico(s)

Supramolecular Chemistry and Complexes

Resumo

Angewandte Chemie International EditionVolume 46, Issue 25 p. 4790-4793 Communication Stereospecific Styrene Enchainment at a Titanium Site within a Helical Ligand Framework: Evidence for the Formation of Homochiral Polystyrene† Klaus Beckerle Dr., Klaus Beckerle Dr. Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, 52056 Aachen, Germany, Fax: (+49) 241-809-2644Search for more papers by this authorRamanujachary Manivannan Dr., Ramanujachary Manivannan Dr. Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, 52056 Aachen, Germany, Fax: (+49) 241-809-2644Search for more papers by this authorBing Lian Dr., Bing Lian Dr. Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, 52056 Aachen, Germany, Fax: (+49) 241-809-2644Search for more papers by this authorGeert-Jan M. Meppelder, Geert-Jan M. Meppelder Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, 52056 Aachen, Germany, Fax: (+49) 241-809-2644Search for more papers by this authorGerhard Raabe Prof. Dr., Gerhard Raabe Prof. Dr. Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52056 Aachen, GermanySearch for more papers by this authorThomas P. Spaniol Dr., Thomas P. Spaniol Dr. Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, 52056 Aachen, Germany, Fax: (+49) 241-809-2644Search for more papers by this authorHenner Ebeling Dr., Henner Ebeling Dr. Freiburger Materialforschungszentrum and Institute of Macromolecular Chemistry, Albert-Ludwigs-Universität Freiburg, Stefan-Meier-Strasse 21, 79104 Freiburg, GermanySearch for more papers by this authorFrederic Pelascini Dr., Frederic Pelascini Dr. Freiburger Materialforschungszentrum and Institute of Macromolecular Chemistry, Albert-Ludwigs-Universität Freiburg, Stefan-Meier-Strasse 21, 79104 Freiburg, GermanySearch for more papers by this authorRolf Mülhaupt Prof. Dr., Rolf Mülhaupt Prof. Dr. Freiburger Materialforschungszentrum and Institute of Macromolecular Chemistry, Albert-Ludwigs-Universität Freiburg, Stefan-Meier-Strasse 21, 79104 Freiburg, GermanySearch for more papers by this authorJun Okuda Prof. Dr., Jun Okuda Prof. Dr. [email protected] Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, 52056 Aachen, Germany, Fax: (+49) 241-809-2644Search for more papers by this author Klaus Beckerle Dr., Klaus Beckerle Dr. Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, 52056 Aachen, Germany, Fax: (+49) 241-809-2644Search for more papers by this authorRamanujachary Manivannan Dr., Ramanujachary Manivannan Dr. Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, 52056 Aachen, Germany, Fax: (+49) 241-809-2644Search for more papers by this authorBing Lian Dr., Bing Lian Dr. Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, 52056 Aachen, Germany, Fax: (+49) 241-809-2644Search for more papers by this authorGeert-Jan M. Meppelder, Geert-Jan M. Meppelder Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, 52056 Aachen, Germany, Fax: (+49) 241-809-2644Search for more papers by this authorGerhard Raabe Prof. Dr., Gerhard Raabe Prof. Dr. Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52056 Aachen, GermanySearch for more papers by this authorThomas P. Spaniol Dr., Thomas P. Spaniol Dr. Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, 52056 Aachen, Germany, Fax: (+49) 241-809-2644Search for more papers by this authorHenner Ebeling Dr., Henner Ebeling Dr. Freiburger Materialforschungszentrum and Institute of Macromolecular Chemistry, Albert-Ludwigs-Universität Freiburg, Stefan-Meier-Strasse 21, 79104 Freiburg, GermanySearch for more papers by this authorFrederic Pelascini Dr., Frederic Pelascini Dr. Freiburger Materialforschungszentrum and Institute of Macromolecular Chemistry, Albert-Ludwigs-Universität Freiburg, Stefan-Meier-Strasse 21, 79104 Freiburg, GermanySearch for more papers by this authorRolf Mülhaupt Prof. Dr., Rolf Mülhaupt Prof. Dr. Freiburger Materialforschungszentrum and Institute of Macromolecular Chemistry, Albert-Ludwigs-Universität Freiburg, Stefan-Meier-Strasse 21, 79104 Freiburg, GermanySearch for more papers by this authorJun Okuda Prof. Dr., Jun Okuda Prof. Dr. [email protected] Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, 52056 Aachen, Germany, Fax: (+49) 241-809-2644Search for more papers by this author First published: 11 June 2007 https://doi.org/10.1002/anie.200700783Citations: 78 † This work was supported by the Fonds der Chemischen Industrie and the Deutsche Forschungsgemeinschaft. R.M. thanks the Alexander von Humboldt Foundation for a postdoctoral fellowship; G.-J.M. thanks the Graduiertenkolleg 440 ("Methoden der asymmetrischen Synthese") for a doctoral fellowship. We thank Prof. M. Schmidt, Mainz University, for kindly measuring MALDI TOF mass spectra. Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat Graphical Abstract Tactful: Titanium catalyst precursors in both optically active, enantiomeric forms have been obtained diastereoselectively, and after activation with methylaluminoxane (MAO) they were used for the stereospecific oligomerization of styrene. The isotactic polystyrenes with a degree of polymerization of up to 45 show measurable optical activity, thus corroborating that enantiomorphic site control is operating in these homogeneous catalysts. Supporting Information Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2002/2007/z700783_s.pdf or from the author. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article. References 1M. Farina, Top. Stereochem. 1987, 17, 1–111. 2 2aP. Pino, J. Am. Chem. Soc. 1987, 109, 6189–6191; 2bP. Pino, M. Galimberti, P. Prada, G. Consiligio, Makromol. Chem. 1990, 191, 1677–1688. 3 3aG. Wulff, Angew. Chem. 1989, 101, 22–38; Angew. Chem. Int. Ed. Engl. 1989, 28, 21–37; 3bY. Okamoto, T. Nakano, Chem. Rev. 1994, 94, 349–372. 4G. W. Coates, R. M. Waymouth, J. Am. Chem. Soc. 1993, 115, 91–98; cf. J. Okuda, Angew. Chem. 1992, 104, 49–50; Angew. Chem. Int. Ed. Engl. 1992, 31, 47–48. 5 5aH. H. Brintzinger, D. Fischer, R. Mülhaupt, B. Rieger, R. M. Waymouth, Angew. Chem. 1985, 97, 507–508; Angew. Chem. Int. Ed. Engl. 1985, 24, 1143–1170; 5bG. W. Coates, Chem. Rev. 2000, 100, 1223–1252. 6W. Kaminsky, A. Ahlers, N. Möller-Lindenhof, Angew. Chem. 1989, 101, 1304–1306; Angew. Chem. Int. Ed. Engl. 1989, 28, 1216–1218. 7 7aP. Pino, M. Galimberti, J. Organomet. Chem. 1989, 370, 1–7; 7bJ. H. Gilchrist, J. E. Bercaw, J. Am. Chem. Soc. 1996, 118, 12021–12028. 8C. Capacchione, A. Proto, H. Ebeling, R. Mülhaupt, K. Möller, T. P. Spaniol, J. Okuda, J. Am. Chem. Soc. 2003, 125, 4964–4965. 9 9aG. Natta, P. Pino, P. Corradini, F. Danusso, E. Mantica, G. Mazzanti, G. Moraglio, J. Am. Chem. Soc. 1955, 77, 1708–1710; 9bG. Natta, P. Corradini, Makromol. Chem. 1955, 16, 77–80; 9cC. Overberger, H. Mark, J. Polym. Sci. 1959, 35, 381–389; 9dR. J. Kern, H. G. Hurst, W. J. Richard, J. Polym. Sci. 1960, 45, 195–204. 10 10aG. J. P. Britovsek, V. C. Gibson, D. F. Wass, Angew. Chem. 1999, 111, 448–468; Angew. Chem. Int. Ed. 1999, 38, 428–447; 10bV. C. Gibson, S. K. Spitzmesser, Chem. Rev. 2003, 103, 283–315. 11 11aC. Capacchione, R. Manivannan, M. Barone, K. Beckerle, R. Centore, L. Oliva, A. Proto, A. Tuzi, T. P. Spaniol, J. Okuda, Organometallics 2005, 24, 2971–2982; 11bK. Beckerle, R. Manivannan, T. P. Spaniol, J. Okuda, Organometallics 2006, 25, 3019–3026. 12 12aJ. Balsells, P. J. Caroll, P. J. Walsh, Inorg. Chem. 2001, 40, 5568–5574; 12bA. Yeori, S. Groysman, I. Goldberg, M. Kol, Inorg. Chem. 2005, 44, 4466–4468; 12cA. Yeori, I. Goldberg, M. Shuster, M. Kol, J. Am. Chem. Soc. 2006, 128, 13062–13063; 12dthe two other diastereomers with cis-β and trans configuration were not observed; for a review on the stereochemistry of complexes containing multidentate ligands, see: P. D. Knight, P. Scott, Coord. Chem. Rev. 2003, 242, 125–143. 13 13aG. J. P. Britovsek, S. A. Cohen, V. C. Gibson, M. van Meurs, J. Am. Chem. Soc. 2004, 126, 10701–10712; 13bM. van Meurs, G. J. P. Britovsek, V. C. Gibson, S. A. Cohen, J. Am. Chem. Soc. 2005, 127, 9913–9923. 14 14aC. Capacchione, F. De Carlo, C. Zannoni, J. Okuda, A. Proto, Macromolecules 2004, 37, 8918–8922; 14bH. Ebeling, Doctoral Thesis, University of Freiburg, 2004. 15Catalyst or ligand residues do not show any optical rotation owing to their low concentration. 16 16aK. Naemura, R. Fukunaga, Chem. Lett. 1985, 1651–1654; 16bH. Tatemitsu, F. Ogura, Y. Nakagawa, M. Nakagawa, K. Naemura, M. Nakazaki, Bull. Chem. Soc. Jpn. 1975, 48, 2473–2483. 17A molecular model based on a so-called octant scheme by Pino et al.[2] suggests that at a Λ,R,R titanium site, styrene inserts via the si (pro-R) face with secondary regiochemistry, resulting in a chain of R configurations; likewise styrene inserts at a Δ,S,S titanium site via the re (pro-S) face forming in a chain of S configurations. 18X-ray crystal structural data for complex rac-2 a: C75H108Cl4O4S4Ti2, Mr=1439.45, T=110 K, crystal dimensions 0.3×0.3×0.2 mm3, monoclinic, P21/c (no. 14), a=9.9475(9), b=30.095(3), c=26.477(2) Å, α=γ=90°, β=100.385(2)°, Z=4, U=7796.6(12) Å3, ρcalcd=1.226 g cm−3, μ=0.494 mm−1, 114 914 collected, 21 765 unique (Rint=0.0619), final R1=0.0618, wR2 [I>2σ(I)]=0.1178, residual electron density extremes were 0.536 and −0.379 e Å−3. CCDC-637376 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif. Citing Literature Volume46, Issue25June 18, 2007Pages 4790-4793 ReferencesRelatedInformation

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