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Volumn 46, Issue 34, 2007, Pages 6508-6513

Rare-earth metal mixed chloro/methyl compounds: Heterogeneous-homogeneous borderline catalysts in 1,3-diene polymerization

Author keywords

Active species; Lanthanides; Neodymium; Polymerization; Ziegler catalysts

Indexed keywords

ALKYLATION; CATALYSTS; COMPLEXATION; POLYMERIZATION; REACTION RATES;

EID: 34548308503     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200604829     Document Type: Article
Times cited : (99)

References (42)
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    • Eds, K. A. Gschneider, Jr, L. Fleming, Elsevier Science Publishers, Dordrecht, chapter 61;
    • a) Z. Shen, J. Ouyang in Handbook on the Physics and Chemistry of Rare Earth (Eds.: K. A. Gschneider, Jr., L. Fleming), Elsevier Science Publishers, Dordrecht, 1987, chapter 61;
    • (1987) Handbook on the Physics and Chemistry of Rare Earth
    • Shen, Z.1    Ouyang, J.2
  • 8
  • 9
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    • X-ray crystallographically characterized rare-earth-metal mixed halide/alkyl complexes feature bulky alkyl and aryl ligands; for examples, see: a C. Eaborn, P. B. Hitchcock, K. Izod, J. D. Smith, J. Am. Chem. Soc. 1994, 116, 12 071;
    • X-ray crystallographically characterized rare-earth-metal mixed halide/alkyl complexes feature bulky alkyl and aryl ligands; for examples, see: a) C. Eaborn, P. B. Hitchcock, K. Izod, J. D. Smith, J. Am. Chem. Soc. 1994, 116, 12 071;
  • 17
    • 28044443397 scopus 로고    scopus 로고
    • Angew. Chem. Int. Ed. 2005, 44, 7473.
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    • Angew1
  • 23
    • 34548314892 scopus 로고    scopus 로고
    • Compound 2b (C24H72Cl2N 4O2Si8Y2, Mr, 922.30) crystallizes from hexane in the triclinic space group P1 with a, 13.1068(4, b, 13.4850(4, c, 16.1737(5) Å, α, 96.766(1, β, 101.307(1, γ, 116.598(1)°, V, 2436.60(13) Å3, dcalcd, 1.257 g cm -3 for Z, 2. Data were collected at 123 K on a BRUKER-AXS 2K CCD system. The structure was solved by direct methods and least-square refinement of the model converged to a final R1, 0.0248 (9778 reflections, I > 2.0σ(I, and wR2, 0.0604 (all data, 11 638 reflections, Compound 4a (C28H 86Cl4N5Nd3O2Si 10, Mr, 1380.44) crystallizes from hexane in the monoclinic space group P21/c wi
    • -3 for Z = 4. Data were collected at 123 K on a BRUKER-AXS 2K CCD system. The structure was solved by direct methods and least-square refinement of the model converged to a final R1 = 0.0302 (11 154 reflections, I > 2.0σ(I)) and wR2 = 0.0550 (all data, 14 571 reflections). CCDC-628824 to CCDC-628826) contain 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.
  • 24
    • 34548325112 scopus 로고    scopus 로고
    • 2-mediated tetrahydrofuran solvent degradation.
    • 2-mediated tetrahydrofuran solvent degradation.
  • 27
    • 33746903178 scopus 로고    scopus 로고
    • Angew. Chem. Int. Ed. 2006, 45, 4858.
    • (2006) Chem. Int. Ed , vol.45 , pp. 4858
    • Angew1
  • 28
    • 34548325111 scopus 로고    scopus 로고
    • Although Ln-NR2→Ln-alkyl transformation is the predominant reaction pathway, significant ligand redistribution reactions and occlusion of nitrogen- and aluminum-containing coproducts is suggested by the microanalytical data. These contaminations N 0.6-1.2, Al 2.1-6.9, which depend on the reaction scale, rule out the formation of pure [Me 2YCl]n or [Me5Nd3Cl 4]n under these reaction conditions
    • n under these reaction conditions.
  • 30
    • 24044545871 scopus 로고    scopus 로고
    • Angew. Chem. Int. Ed. 2005, 44, 5303.
    • (2005) Chem. Int. Ed , vol.44 , pp. 5303
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  • 33
  • 37
    • 18844374180 scopus 로고    scopus 로고
    • 3-mediated Ln-butenyl(allyl)→Ln-Me(aluminate) transformation might occur under these reaction conditions: W. J. Evans, S. A. Kozimor, J. C. Brady, B. L. Davis, G. W. Nyce, C. A. Seibel, J. W. Ziller, R. J. Doedens, Organometallics 2005, 24, 2269.
    • 3-mediated Ln-butenyl(allyl)→Ln-Me(aluminate) transformation might occur under these reaction conditions: W. J. Evans, S. A. Kozimor, J. C. Brady, B. L. Davis, G. W. Nyce, C. A. Seibel, J. W. Ziller, R. J. Doedens, Organometallics 2005, 24, 2269.
  • 39
    • 34548323058 scopus 로고    scopus 로고
    • We were not able to control the chlorination of [Nd(AlMe 4)3] to generate pure [Me2NdCl] n. Separation of AlMe3 during the chlorination was unequivocally proven by 13C and 27Al NMR spectroscopic examination of the reaction of [Y(AlMe4)3] with Ph 3CCl; [Nd(AlMe4)3]/Ph3CCl (1:1) in hexane gave a solid 5d″ which polymerizes isoprene comparably to 5d and 5d′
    • 3CCl (1:1) in hexane gave a solid 5d″ which polymerizes isoprene comparably to 5d and 5d′.
  • 40
    • 34548298247 scopus 로고    scopus 로고
    • Similar molecular weight distributions have been reported for the binary systems [Nd(OC6H3iPr-2,6)3(AlMe 3)2]/Et2AlCl (Mn/ Mw, 2.03)[4] and [Nd(neopentanolate) 3(AlMe3)3]/Et2AlCl (M n/Mw, 1.74)[4] as well as [Nd(AlMe 4)3]/Et2AlCl immobilized on MCM-48 Mn/Mw, 1.33-1.88, 5
    • [5]
  • 41
    • 34548300338 scopus 로고    scopus 로고
    • 4] was previously described to not catalyze the polymerization of isoprene; Ref. [8].
    • 4] was previously described to not catalyze the polymerization of isoprene; Ref. [8].


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