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(a) Exceptions are the electrochemical reductions of iodobenzene and 4-methyliodobenzene where the mechanism shifts from concerted to stepwise upon increasing the driving force.
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10344253261
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(l) the structure of 5-bromo-8-methoxypsoralen studied in ref 4k is as follows: (Equation Presented)
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5g of the redox catalysis approach, using steady-state techniques or optical detection instead of cyclic voltammetry, reports the possibility to reach somewhat higher rate constants.
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RN1 substitution, key references are the following.
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[Ar•]•-) may be considered as compensating each other.
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(a) Besides the case of 4-cyano-chlorobenzene, treated in details in ref 12, an indication that bond bending effects may play an important role is given in ref 11, where it is shown on the base of DFT calculations that the transition states are more bended than the initial state and that the activation energy calculated with no geometrical constraint is smaller than the activation energy with forced planarity (corresponding to a conical intersection). However, the comparison seems uncertain, if not inaccurate, since a single reference method was used in these calculations (B3LYP), as strongly emphasized in many cases when conical intersections are involved (see, for example, refs 14b-d).
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67
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10344248139
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0) + 0.44. Free enthlapies of transfer from water to DMF for the various ions were obtained from ref 15, while standard free enthalpies of formation for chlorine, bromine, chloride and bromide were collected from ref 19b.
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70
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10344232628
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note
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The same remark also applies to Figure 7 in ref 5g.
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