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Organometallics
Volumn 28, Issue 14, 2009, Pages 4048-4055
Unusual reactivity of N, N,N′,N′-tetramethylethylenediamine- coordinated neutral nickel(II) polymerization catalysts
Author keywords

[No Author keywords available]
Indexed keywords

ACTIVATION PARAMETER; ALKYL COMPLEXES; AQUEOUS CONDITION; BINDING MODES; CATALYST PRECURSORS; DEACTIVATION MECHANISM; DEACTIVATION PATHWAYS; DECOMPOSITION REACTION; EQUILIBRIUM MIXTURES; FREE SOLUTIONS; METHYL COMPLEXES; NEUTRAL NICKEL; NMR CHEMICAL SHIFTS; NMR TUBES; OLEFIN POLYMERIZATION CATALYSIS; ORDERS OF MAGNITUDE; POLYMERIZATION CATALYSTS; PSEUDO-FIRST-ORDER RATE CONSTANT; REACTION UNDER; SALICYLALDIMINES; SOLUTION NMR; SPECTROSCOPIC STUDIES; TETRAMETHYLETHYLENEDIAMINE;
EID: 67651033646     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om900198c     Document Type: Article
Times cited : (12)
References (79)
  • 5
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    • (a) Johnson, L. K.; Bennett, A. M. A.; Ittel, S. D.; Wang, L.; Parthasarathy, A.; Hauptman, E.; Simpson, R. D.; Feldman, J.; Coughlin, E. B. (DuPont) WO98/30609, 1998.
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    • (g) Bastero, A.; KoIb, L.; Wehrmann, P.; Bauers, F. M.; Göttker gen. Schnetmann, I.; Monteil, V.; Thomann, R.; Chowdhry, M. M.; Mecking, S. Polym. Mat. Sci. Eng. 2004, 90, 740-741.
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    • For computational studies see: a
    • For computational studies see: (a) Chan, M. S. W.; Deng, L.; Ziegler, T. Organometallics 2000, 19, 2741-2750.
    • (2000) Organometallics , vol.19 , pp. 2741-2750
    • Chan, M.S.W.1    Deng, L.2    Ziegler, T.3
  • 66
    • 0040796284 scopus 로고    scopus 로고
    • 2NiMe(OMe)] as a precursor see: Klein, H.-F. Inorg. Chim. Acta 1996, 248, 111-114.
    • 2NiMe(OMe)] as a precursor see: Klein, H.-F. Inorg. Chim. Acta 1996, 248, 111-114.
  • 68
    • 35448976067 scopus 로고    scopus 로고
    • 1O)H: (a) Skupov, K. M.; Marella, P. R.; Simard, M.; Yap, G. P. A.; Allen, N; Conner, D.; Goodall, B. L.; Claverie, J. P. Macromol. Rapid Commun. 2007, 28, 2033-2038.
    • 1O)H: (a) Skupov, K. M.; Marella, P. R.; Simard, M.; Yap, G. P. A.; Allen, N; Conner, D.; Goodall, B. L.; Claverie, J. P. Macromol. Rapid Commun. 2007, 28, 2033-2038.
  • 70
    • 67651038401 scopus 로고    scopus 로고
    • Key 1H NMR resonances observed in methanol-d4 at 25 °C: 10.19 and -1.64, HC=N- and Ni(II)-CH3, 1- κ2-tmeda, 7.69, 2.40, 2.32, and -0.72, HC=N, H 3C)2NCH2}1/2, H3C) 2NCH2) 1/2, and Ni(II)-CH3, 1-κ1-tmeda, 7.62 and -1.28, HC=N- and Ni(II)-CH3, 1-O(D)CD3) ppm. Resonances of free tmeda were observed at 2.01, H3C)2NCH2} 1/2) and 2.26, H3C)2NCH2)1/2) ppm. Equilibrium constants according to 1H NMR spectra (see Scheme 1, K Me,1 =5.3 × 10-3(△Go=13 kJ mor-1, KMe=KMe,1/KMe,2=8 × 10-3(△Go=14 kJ mol-1, Key 1H NMR resonances (imine/Ni(II)-CH3
    • 8 solution.
  • 71
    • 67651079078 scopus 로고    scopus 로고
    • 9)], an observation that underlines the particular binding properties of the bidentate tmeda ligand.
    • 9)], an observation that underlines the particular binding properties of the bidentate tmeda ligand.
  • 72
    • 67651016728 scopus 로고    scopus 로고
    • 2-tmeda and 1-dmso) for temperatures from 55 to 80 °C (Figure S5).
    • 2-tmeda and 1-dmso) for temperatures from 55 to 80 °C (Figure S5).
  • 73
    • 67651057324 scopus 로고    scopus 로고
    • mix applied in the 2D spectra.
    • mix applied in the 2D spectra.
  • 74
    • 67651054046 scopus 로고    scopus 로고
    • An averaged value of 1.9 × 10-4 M-1 s -1 was calculated independently for khydr,1-tmeda from initial rates of methane formation rCH3D and initial concentrations of 1-tmeda and D2O according to khydr,1-tmeda, r CH3D/[1-tmeda]t, 0[D2O]t, 0
    • t = 0).
  • 75
    • 67651019839 scopus 로고    scopus 로고
    • Comparison of the average value of 2.4 × 10-4 s-1 for kins,Me,1-tmeda with k*ins,Me.1-dmso ≈ 4.5 × 10-4 s-1 at [C2H4] ≈ 0.1 M (calculated from kins,Me,1-dmso, 6.8 × 10-4 s-1 at [C2H4] ≈ 0.15 M; see ref 13) indicates that activation of 1-tmeda may occur preferentially from 1-dmso instead of 1- κ2-tmeda under the conditions studied. Considering 1- κ2-tmeda as a dormant and 1-dmso as a reactive component toward ethylene under the conditions studied, independent calculation of a corrected pseudo-first-order insertion rate constant according to k ins,Me,1- tmeda =k*ins,Me,1.dmso (1/(1, tmeda]free{KMe328 K, dmso-d6, 1, yields k*ins,Me,1-tmeda=3.4 × 10-4 s-1, 1-tmeda]t
    • -2).

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