Kinetic model for the reaction of cobalt porphyrins with olefins under free radical conditions

Organometallics

Volumn 15, Issue 1, 1996, Pages 222-235

  Gridnev, Alexei A ^a   Ittel, Steven D ^a   Fryd, Michael ^a   Wayland, Bradford B ^b  

^a DUPONT COMPANY   (United States)

^b UNIVERSITY OF PENNSYLVANIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000738019     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om9502998     Document Type: Article

References (102)

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60. 12
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81. Cage effects have been demonstrated to play an important role in a number of organometallic systems noted below, but in this particular study, all of the work was done in a single, low-viscosity medium. We do not believe cage effects to have played a role in the observations reported here. See, for instance, ref 13e and: (a) Koenig, T.; Fischer, H. In Free Radicals; Kochi, J., Ed.; Wiley: New York, 1973; Vol. 1. (b) Gerards, L. E. H.; Bulthuis, H.; de Bolster, M. W. G.; Balt, S. Inorg. Chim. Acta 1991, 190, 47. (c) Bagdasar'yan, Kh. S. Usp. Khim. 1984, 53, 1073; Russ. Chem. Rev. (Engl. Transl.) 1984, 53, 1100. (d) Koenig, T. W.; Finke, R. G. J. Am. Chem. Soc. 1988, 110, 2657. (e) Kim, S.-H.; Chen, H. L.; Feilchenfeld, N.; Halpern, J. J. Am. Chem. Soc. 1988, 110, 3120
82. Cage effects have been demonstrated to play an important role in a number of organometallic systems noted below, but in this particular study, all of the work was done in a single, low-viscosity medium. We do not believe cage effects to have played a role in the observations reported here. See, for instance, ref 13e and: (a) Koenig, T.; Fischer, H. In Free Radicals; Kochi, J., Ed.; Wiley: New York, 1973; Vol. 1. (b) Gerards, L. E. H.; Bulthuis, H.; de Bolster, M. W. G.; Balt, S. Inorg. Chim. Acta 1991, 190, 47. (c) Bagdasar'yan, Kh. S. Usp. Khim. 1984, 53, 1073; Russ. Chem. Rev. (Engl. Transl.) 1984, 53, 1100. (d) Koenig, T. W.; Finke, R. G. J. Am. Chem. Soc. 1988, 110, 2657. (e) Kim, S.-H.; Chen, H. L.; Feilchenfeld, N.; Halpern, J. J. Am. Chem. Soc. 1988, 110, 3120
83. Cage effects have been demonstrated to play an important role in a number of organometallic systems noted below, but in this particular study, all of the work was done in a single, low-viscosity medium. We do not believe cage effects to have played a role in the observations reported here. See, for instance, ref 13e and: (a) Koenig, T.; Fischer, H. In Free Radicals; Kochi, J., Ed.; Wiley: New York, 1973; Vol. 1. (b) Gerards, L. E. H.; Bulthuis, H.; de Bolster, M. W. G.; Balt, S. Inorg. Chim. Acta 1991, 190, 47. (c) Bagdasar'yan, Kh. S. Usp. Khim. 1984, 53, 1073; Russ. Chem. Rev. (Engl. Transl.) 1984, 53, 1100. (d) Koenig, T. W.; Finke, R. G. J. Am. Chem. Soc. 1988, 110, 2657. (e) Kim, S.-H.; Chen, H. L.; Feilchenfeld, N.; Halpern, J. J. Am. Chem. Soc. 1988, 110, 3120
84. Cage effects have been demonstrated to play an important role in a number of organometallic systems noted below, but in this particular study, all of the work was done in a single, low-viscosity medium. We do not believe cage effects to have played a role in the observations reported here. See, for instance, ref 13e and: (a) Koenig, T.; Fischer, H. In Free Radicals; Kochi, J., Ed.; Wiley: New York, 1973; Vol. 1. (b) Gerards, L. E. H.; Bulthuis, H.; de Bolster, M. W. G.; Balt, S. Inorg. Chim. Acta 1991, 190, 47. (c) Bagdasar'yan, Kh. S. Usp. Khim. 1984, 53, 1073; Russ. Chem. Rev. (Engl. Transl.) 1984, 53, 1100. (d) Koenig, T. W.; Finke, R. G. J. Am. Chem. Soc. 1988, 110, 2657. (e) Kim, S.-H.; Chen, H. L.; Feilchenfeld, N.; Halpern, J. J. Am. Chem. Soc. 1988, 110, 3120
85. Cage effects have been demonstrated to play an important role in a number of organometallic systems noted below, but in this particular study, all of the work was done in a single, low-viscosity medium. We do not believe cage effects to have played a role in the observations reported here. See, for instance, ref 13e and: (a) Koenig, T.; Fischer, H. In Free Radicals; Kochi, J., Ed.; Wiley: New York, 1973; Vol. 1. (b) Gerards, L. E. H.; Bulthuis, H.; de Bolster, M. W. G.; Balt, S. Inorg. Chim. Acta 1991, 190, 47. (c) Bagdasar'yan, Kh. S. Usp. Khim. 1984, 53, 1073; Russ. Chem. Rev. (Engl. Transl.) 1984, 53, 1100. (d) Koenig, T. W.; Finke, R. G. J. Am. Chem. Soc. 1988, 110, 2657. (e) Kim, S.-H.; Chen, H. L.; Feilchenfeld, N.; Halpern, J. J. Am. Chem. Soc. 1988, 110, 3120
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92. 2. Using the observed concentration of LCo-cyclopentyl (0.0052 M) as the concentration of MAN, the value [cyclopenteney]/ [MAN] = 380 has been calculated. It is in reasonable agreement with the remainder of the points obtained by direct addition of MAN to the reaction, thereby indicating the very rapid reaction of MAN with the hydridocobalt porphyrin complex. The point appears to be low, but the considerable error in this particular measurement makes any attempt at explanation difficult.
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