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In the absence of iron fluoride or hydride there was no sign of reaction (= 1%) between any of the substrates and trisubstituted silanes.
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note
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The HDF reaction does not take place in more polar solvents such as DMF or HMPA. This may be due to reaction between the iron(II) hydride complex and these solvents.
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19744375162
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note
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Another possibility is that the active species is a silyl complex. Unfortunately, our several attempts to isolate a diketiminate iron(II) silyl complex independently have so far failed. The intermediacy of silyl cations (cf. ref 13) or silyl radicals is inconsistent with the regioselectivity of C-F activation and with the first-order dependence of the initial rate on iron concentration.
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110
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19744378711
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note
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3CH, 0.47 molar equiv) is used as the radical trap (48% conversion under the same conditions).
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111
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19744377723
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note
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18a
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113
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19744370965
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note
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2-complexes of perfluoronaphthalene and perfluoropyridine (see ref 7b). In these nickel systems, C-F activation of perfluoropyridine occurred at C2 rather than at C4 as observed in the iron-catalyzed process demonstrated here. In our system, electronic absorption spectra show no substantial coordination of perfluorocarbons to the iron(II) diketiminate complex (see text and Figure 4).
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116
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19744365964
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note
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41
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19744375777
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note
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There is a large disparity between the ability of perfluoroarenes to be reduced in the gas and solution phases. For example, the gas phase electron affinities of hexafluorobenzene and octafluorotoluene are favorable with values of 0.52(1) and 0.94(1) eV, respectively, but both have highly negative irreversible reduction potentials in THF solution (-3.0 and -2.95 V vs ferrocene; see refs 48 and 4b). In our mechanistic analysis, we use the solution values and assume that the overpotentials are not excessive (more than a few hundred millivolts).
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121
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note
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A similar hydride insertion/β-fluoride elimination mechanism is unlikely to operate in the HDF of perfluoroarenes. Such a mechanism would involve breaking the aromaticity of the substrate and therefore is expected to increase the activation barrier relative to olefinic C-F activation. This is inconsistent with HDF of perfluoroarenes occurring at lower temperatures than for olefinic substrates.
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122
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19744380318
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note
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2 does not react with 1-hexene: we conclude that hydride formation must occur before catalysis proceeds.
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123
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