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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
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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.
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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
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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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