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Volumn 122, Issue 5, 2000, Pages 751-761

Zirconium-mediated metathesis of imines: A study of the scope, longevity, and mechanism of a complicated catalytic system

Author keywords

[No Author keywords available]

Indexed keywords

ACETYLENE; IMINE; KETAMINE; ZIRCONIUM;

EID: 0034624392     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja992869r     Document Type: Article
Times cited : (108)

References (38)
  • 17
    • 12944326666 scopus 로고    scopus 로고
    • note
    • A slow side reaction between diphenylacetylene and the reactant and product imines was catalyzed by 6b. This resulted in the complete consumption of diphenylacetylene over a period of 4 days, leaving diazametallacycles 3 as the predominant Zr-containing species.
  • 18
    • 12944325614 scopus 로고    scopus 로고
    • note
    • eq value of 7.4 for the 6a/3a interconversion at 70°C is incorrect because of the misinterpretation of spectroscopic data. The equilibrium value was remeasured at 75°C at three different concentrations of 3a, and the spectral data were compared with those for authentic samples of 6a and 3a.
  • 25
    • 12944322026 scopus 로고    scopus 로고
    • 2). The details of this study have been published independently (J. Organomet. Chem., 1999, 591, 2).
    • (1999) J. Organomet. Chem. , vol.591 , pp. 2
  • 26
    • 12944298072 scopus 로고    scopus 로고
    • note
    • Complex 10a was not chosen as the catalyst precursor for the kinetic measurements because its imine adducts analogous to 3 exist as pairs of diastereomers. It was thought that this would further complicate the already complex system.
  • 27
    • 12944280059 scopus 로고    scopus 로고
    • note
    • eq measurements in eq 3 predict that, at equilibrium, less than 10% of 6b should be converted to diazametallacyclobutanes 3.
  • 28
    • 12944303443 scopus 로고    scopus 로고
    • McKinney, R. J.; Weigert, F. J. Project SERAPHIM. Program number 1b-1407.8
    • The FORTRAN programs GEAR and GIT (v. 2.1) were used for all kinetic simulations. (a) McKinney, R. J.; Weigert, F. J. Project SERAPHIM. Program number 1b-1407.8. (b) Weigert, F. J. Comput. Chem. 1987, 11, 273. (c) Stabler, R. N.; Chesick, J. Int. J. Chem. Kinet. 1978, 10, 461.
  • 29
    • 0023593589 scopus 로고
    • The FORTRAN programs GEAR and GIT (v. 2.1) were used for all kinetic simulations. (a) McKinney, R. J.; Weigert, F. J. Project SERAPHIM. Program number 1b-1407.8. (b) Weigert, F. J. Comput. Chem. 1987, 11, 273. (c) Stabler, R. N.; Chesick, J. Int. J. Chem. Kinet. 1978, 10, 461.
    • (1987) Comput. Chem. , vol.11 , pp. 273
    • Weigert, F.J.1
  • 30
    • 84986849950 scopus 로고
    • The FORTRAN programs GEAR and GIT (v. 2.1) were used for all kinetic simulations. (a) McKinney, R. J.; Weigert, F. J. Project SERAPHIM. Program number 1b-1407.8. (b) Weigert, F. J. Comput. Chem. 1987, 11, 273. (c) Stabler, R. N.; Chesick, J. Int. J. Chem. Kinet. 1978, 10, 461.
    • (1978) Int. J. Chem. Kinet. , vol.10 , pp. 461
    • Stabler, R.N.1    Chesick, J.2
  • 31
    • 12944320135 scopus 로고    scopus 로고
    • note
    • Further examples of concentration vs time plots for the experimental and kinetic data are available as Supporting Information.
  • 32
    • 12944304966 scopus 로고    scopus 로고
    • note
    • eq value for the interconversion of 6b and 3d.
  • 33
    • 12944303444 scopus 로고    scopus 로고
    • note
    • The parameters chosen initially for the experimental data fitting were based on rate constants experimentally determined from previous kinetic studies of the stoichiometric reactions. These parameters were then adjusted to obtain the best fit for the eight experimental runs. Final optimization of the model was accomplished by application of a nonlinear least-squares fitting routine. Simulations were allowed to converge, then restarted at the convergence point. This process was repeated until no further variations were seen in the rate constants. Rate constants obtained after convergence were still in agreement with independently measured equilibrium and rate constants.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.