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Volumn 28, Issue 5, 2009, Pages 1303-1308

Theoretical analysis of the catalytic cycle of a nickel cross-coupling process: Application of the energetic span model

Author keywords

[No Author keywords available]

Indexed keywords

CATALYTIC CYCLES; CROSS COUPLINGS; ENERGY PROFILES; FIRST-ORDER KINETICS; HIGH CONCENTRATIONS; KINETIC BEHAVIORS; ORGANOZINC REAGENTS; PRODUCT RELEASE; TRANSITION STATE; ZERO-ORDER KINETICS;

EID: 64749096149     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om800772g     Document Type: Article
Times cited : (67)

References (32)
  • 1
    • 0038770816 scopus 로고    scopus 로고
    • See for example: (a) Maseras, F, Lledos, A, Eds, Kluwer Academic Publishers: Amsterdam
    • See for example: (a) Maseras, F.; Lledos, A., Eds. Computational Modeling of Homogeneous Catalysis; Kluwer Academic Publishers: Amsterdam, 2002.
    • (2002) Computational Modeling of Homogeneous Catalysis
  • 2
    • 0004104842 scopus 로고    scopus 로고
    • Truhlar, D. G, Morokuma, K, Eds, American Chemical Society: Washington, DC
    • (b) Truhlar, D. G.; Morokuma, K., Eds. Transition State Modeling for Catalysis; American Chemical Society: Washington, DC, 1998.
    • (1998) Transition State Modeling for Catalysis
  • 22
    • 11344285812 scopus 로고    scopus 로고
    • Schrodinger, LLC: Portland, Oregon
    • Jaguar 5.5; Schrodinger, LLC: Portland, Oregon, 2003.
    • (2003) Jaguar 5.5
  • 31
    • 11844278498 scopus 로고    scopus 로고
    • Our paper focused on the reaction with COD. See for example ref 4 and (a) Bercot, E. A, Rovis, T J. Am. Chem. Soc. 2005, 127, 247
    • Our paper focused on the reaction with COD. See for example ref 4 and (a) Bercot, E. A.; Rovis, T J. Am. Chem. Soc. 2005, 127, 247.
  • 32
    • 38549132389 scopus 로고    scopus 로고
    • Johnson, J. B; Rovis, T. Angew. Chem, Int. Ed. 2008, 47, 840. However, as one referee pointed out, in the original experiment of Johnson et al.,4 changes in the concentration of 4-fluorostyrene, which is a better ligand than COD, do not change the TOF of the cycle, making this apparently contradictory with the TDTS (TSLS) found in our work. In fact, our calculations show that the use of styrene instead of COD in complex 1 results in a 18.6 kcal/mol more stable complex (E+ZPE, This fact indicates that adding styrene will stabilize the Ni-ligand bond and will pull down all the states of the cycle that contain this ligand, including the ligand substitution (TSLS, In the cycle studied in the paper, TSLS has a slightly larger degree of TOF control than the reductive elimination, TS RE see Figure 3, But a small quantity of styrene will lower the energy of TSLS, thus converting the second more influential transition sta
    • RE is the TDTS, changes in the styrene concentration will not affect the rate of reaction. However, the addition of a catalytic quantity of styrene may accelerate the cycle by changing the TDTS from the ligand substitution to the reductive elimination.


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