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31P NMR spectrum closely matched that observed in a H NMR spectrum for an authentic mixture of 2 and 3.
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31P NMR spectrum closely matched that observed in a H NMR spectrum for an authentic mixture of 2 and 3.
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By this reasoning, two atropisomers are expected and only two isomers are experimentally observed
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By this reasoning, two atropisomers are expected and only two isomers are experimentally observed.
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p.a is not a good reflection of the formal reduction potential, E°, because of an exceptionally fast chemical reaction (substitution) following the electrochemical event (EC) mechanism. This would shift the anodic peak negative.
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6A and 6B are almost certainly in equilibrium, based on our previous examination of intraannular and interannular isomerization rates for naphthalenes.
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6A and 6B are almost certainly in equilibrium, based on our previous examination of intraannular and interannular isomerization rates for naphthalenes.
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Originally this is formed as the kinetic isomer in which O is oriented away from the phosphine. Over time this rearranges to the thermodynamic isomer in which the oxygen is oriented toward the phosphine
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Originally this is formed as the kinetic isomer in which O is oriented away from the phosphine. Over time this rearranges to the thermodynamic isomer in which the oxygen is oriented toward the phosphine.
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A second, small coupling constant is also present of J = 5.9 Hz.
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A second, small coupling constant is also present of J = 5.9 Hz.
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The half-life for benzene substitution at 22°C is largely unaffected by either the nature or the concentration of the incoming ligand.
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The half-life for benzene substitution at 22°C is largely unaffected by either the nature or the concentration of the incoming ligand.
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The approach of fluorobenzene to the agent [W] was traced for two pathways, with the reaction coordinate being the W-F or W-H distance, respectively. The first pathway led to a well-defined equilibrium complex A and a transition state B° from which the CF activated product derives. The second pathway led smoothly to the CH activation product. Since pure density functionals are known to underestimate activation barriers (see Stanton, R. V, Merz, Jr, K. M. J. Chem. Phys. 1994, 100, 434) and LSDA in particular overestimates binding energy in stable molecules, and because an admixture of HF exchange into the density functional, such as is done in the B3LYP formulation, improves estimates of barrier heights relative to those obtained by pure DFT functionals, we retraced the path with B3LYP/LANL2DZ model chemistry calculations. This produced a shallow minimum with an activation barrier no greater than 1 kcal/mol. We reoptimized the structure of the wea
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The approach of fluorobenzene to the agent [W] was traced for two pathways, with the reaction coordinate being the W-F or W-H distance, respectively. The first pathway led to a well-defined equilibrium complex A and a transition state B° from which the CF activated product derives. The second pathway led smoothly to the CH activation product. Since pure density functionals are known to underestimate activation barriers (see Stanton, R. V.; Merz, Jr, K. M. J. Chem. Phys. 1994, 100, 434) and LSDA in particular overestimates binding energy in stable molecules, and because an admixture of HF exchange into the density functional, such as is done in the B3LYP formulation, improves estimates of barrier heights relative to those obtained by pure DFT functionals, we retraced the path with B3LYP/LANL2DZ model chemistry calculations. This produced a shallow minimum with an activation barrier no greater than 1 kcal/mol. We reoptimized the structure of the weak complex, constraining the C-H and H-W distances and the C-H-W angle to the values obtained in B3LYP/ LANL2DZ. The energies quoted in the text for the CH complex and the transition state on the path toward the CH activated structure are LSDA/ LANL2DZ values obtained at these constrained structures. We are confident in the values of the energies of these points along the CH activation path within 5 kcal/mol or less and consider that the values quoted are upper bounds to the values at corresponding points on the fully optimized path.
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