Self-Immobilizing Precatalysts: Norbornene-Bridged Zirconium ansa-Metallocenes
FULL PAPERS
terminated and the polymers treated as previously de-
scribed.
Engl. 1995, 34, 1143–1170; d) M. Bochmann, J. Chem.
Soc. Dalton Trans. 1996, 225–270; e) W. Kaminsky, M.
Arndt, Adv. Polym. Sci. 1997, 127, 143–187; f) L. Re-
sconi, L. Cavallo, A. Fait, F. Piemontesi, Chem. Rev.
2000, 100, 1253–1346; g) S. D. Ittel, L. K. Johnson, M.
Brookhart, Chem. Rev. 2000, 100, 1169–1204; h) H. G.
Alt, A. Kçppl, Chem. Rev. 2000, 100, 1205–1222;
i) G. W. Coates, Chem. Rev. 2000, 100, 1223–1252; j) W.
Kaminsky, J. Polym. Sci. Part A: Polym. Chem. 2004,
42, 3911–3921; k) W. Kaminsky, J. Chem. Soc. Dalton
Trans. 1998, 1413–1418; l) G. Erker, G. Kehr, R. Froh-
lich, Coord. Chem. Rev. 2006, 250, 36–46.
NMR Analysis
13C NMRspectra of the polymers were recorded in C D2Cl4
2
at 1038C on a Bruker Avance-400 spectrometer operating at
100.58 MHz (internal chemical shift reference: 1% hexame-
thyldisiloxane). Conditions: 10 mm probe; 908 pulse angle;
64 K data points zero-filled to 128 K before FT; acquisition
time 8.57 s; relaxation delay 20 s; 3–4 K transients. Proton
broad-band decoupling was achieved using bi_waltz16_32
power-gated decoupling. In the insert of Figure 1b, the FID
was processed using a Gaussian multiplication (line broad-
ening À0.8 Hz, Gaussian broadening 0.02).
[2] a) G. G. Hlatky, Chem. Rev. 2000, 100, 1347–1376;
b) G. Fink, B. Steinmetz, J. Zechlin, C. Przybyla, B.
Tesche, Chem. Rev. 2000, 100, 1377–1390; c) M. R. Ri-
beiro, A. Deffieux, M. F. Portela, Ind. Eng. Chem. Res.
1997, 36, 1224–1237; d) W. Kaminsky, D. Arrowsmith,
C. Strübel, J. Polym. Sci. Part A: Polym. Chem. 1999,
37, 2959–2968; e) R. Goertzki, G. Fink, B. Tesche, B.
Steinmetz, R. Rieger, W. Uzick, J. J. Polym. Sci. Part
A: Polym.Chem. 1999, 37, 677–682; f) P. Roos, G. G.
Meier, J. J. C. Samson, G. Weicker, K. R. Westerterp,
Macromol. Rapid Commun. 1997, 18, 319–324; g) K.
Soga, T. Ari, B. H. Hoang, T. Uozumi, Macromol.
Rapid Commun. 1995, 16, 905–911; h) C. Alonso, A.
AntiÇolo, F. Carrillo-Hermosilla, P. Carrión, A. Otero,
J. Sancho, E. VillaseÇor, J. Mol. Catal. Part A 2004,
220, 285–295; i) M. Sacchetti, S. Pasquali, G. Govoni,
US Patent 5,698,487, 1997; j) Y. V. Kissin, T. E. Nowlin,
R. I. Mink, A. J. Brandolini, Macromolecules 2000, 33,
4599–4601; k) W. Ochedzan-Siodlak, M. Nowakowska,
Eur. Polym. J. 2005, 41, 941–947; l) J. R. Severn, J. C.
Chadwick, R. Duchateau, N. Friederichs, Chem. Rev.
2005, 105, 4073–4147, and references cited therein;
m) P. Carrión, F. Carrillo-Hermosilla, C. Alonso-
Moreno, A. Otero, A. AntiÇolo, J. Sancho, E. Villase-
Çor, J. Mol. Catal. Part A 2006, 258, 236–245; n) Tailor-
Made Polymers: Via Immobilization of Alpha-Olefin
Polymerization Catalysts, (Eds.: J. R. Severn, J. C.
Chadwick), Wiley-VCH, Weinheim, 2008.
Molar Mass Determination
Gel permeation chromatographic analyses of the polymers
were performed at a flow rate of 0.8 mLminÀ1 in 1,2,4-tri-
chlorobenzene at 1458C using a Waters GPC 2000 instru-
ment with a refractive index detector (Columns: 3 PL Gel
Olexis + 1 F (2 mm). Molar masses were determined with
reference to a polystyrene calibration curve (processing
method: PS 145 Univ Lin Sep 07).
INAA (Instrumental Neutron Activation Analysis)
The samples obtained as described in Table 4 were sealed in
polyethylene plastic containers under an inert atmosphere
and analyzed by the INAA technique. Self-immobilized cat-
alysts 1 and 2 contain 0.997 and 1.454 mmol of Zr, respec-
tively.
Supporting Information
Mechanism for spiro by-product formation, complete crys-
tallographic tables, general remarks and pictures about the
equipment used, spectroscopic and analytical data for the
synthesized compounds are reported in the Supporting In-
formation file.
[3] a) J. C. W. Chien, Topics in Catal. 1999, 7, 23–36, and
references cited therein; b) W. Kaminsky, H. Winkel-
bach, Topics in Catal. 1999, 7, 61–67.
Acknowledgements
[4] a) B. Peifer, W. Milius, H. G. Alt, J. Organomet. Chem.
1998, 553, 205–220; b) H. G. Alt, M. Jung, G. Kehr, J.
Organomet. Chem. 1998, 562, 153–181; c) H. G. Alt, M.
Jung, J. Organomet. Chem. 1998, 562, 229–253;
d) H. G. Alt, M. Jung, J. Organomet. Chem. 1999, 580,
1–16; e) H. G. Alt, J. Chem. Soc. Dalton Trans. 1999,
1703–1710, and references cited therein; f) H. G. Alt,
Dalton Trans. 2005, 3271–3276; g) D. Zhang, G. Xin
Jin, J. Appl. Catal. Part A 2004, 262, 85–91.
[5] a) E. Polo, R. M. Bellabarba, G. Prini, O. Traverso,
M. L. H. Green, J. Organomet. Chem. 1999, 577, 211–
218; b) E. Polo, S. Losio, F. Forlini, P. Locatelli, A. Pro-
vasoli, M. C. Sacchi, Macromol. Chem. Phys. 2002, 203,
1859–1865; c) E. Polo, S. Losio, G. Zecchi, F. Bertini,
M. C. Sacchi, Macromol. Rapid Commun. 2004, 25,
1845–1850; d) E. Polo, S. Losio, F. Forlini, P. Locatelli,
M. C. Sacchi, Macromol. Symp. 2004, 213, 89–99; e) S.
Losio, G. Zecchi, F. Bertini, M. C. Sacchi, V. Bertolasi,
E. Polo, Macromolecules 2005, 38, 7231–7240.
The authors warmly thank Dr. Luigi Bergamaschi (INAA
analyses) from Istituto Nazionale di Ricerca Metrologica
(INRIM Pavia), Mr. G. Zannoni (NMR experiments), and
Mr. A. Giacometti Schieroni (GPC analysis) from ISMAC.
Dr. Simona Losio’s (ISMAC) precious experimental contri-
bution is also gratefully acknowledged. We also thank Prof.
Malcolm L. H. Green of Oxford University (UK) for helpful
discussion and synthetic suggestions.
References
[1] a) R. F. Jordan, Adv. Organomet. Chem. 1991, 32, 325–
387; b) P. C. Mçhring, N. J. Coville, J. Organomet.
Chem. 1994, 479, 1–29; c) H.-H. Brintzinger, D. Fisch-
er, R. Mülhaupt, B. Rieger, R. M. Waymouth, Angew.
Chem. 1995, 107, 1255–1283; Angew. Chem. Int. Ed.
Adv. Synth. Catal. 2008, 350, 1544 – 1556
ꢀ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1555