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This step might be preceded by coordination of the azobenzene in an η1 binding mode; see ref 22o
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1 binding mode; see ref 22o.
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8344267913
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tBuFeNHPh as a product.
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tBuFeNHPh as a product.
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69
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34447126032
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‡ = -36 ± 4 eu. However, the induction period suggests a chain mechanism (discussed at length below), in which the rate constants do not reflect elementary steps. Therefore, these apparent activation parameters should be interpreted only with the greatest caution.
-
‡ = -36 ± 4 eu. However, the induction period suggests a chain mechanism (discussed at length below), in which the rate constants do not reflect elementary steps. Therefore, these apparent activation parameters should be interpreted only with the greatest caution.
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70
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34447116013
-
-
D is 0.95 ± 0.23, and the value near unity is consistent with loss of deuterium label.
-
D is 0.95 ± 0.23, and the value near unity is consistent with loss of deuterium label.
-
-
-
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73
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34447116646
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tBuFeNPhNHPh. Many other control experiments were also performed to verify that the products do not react with each other or with byproducts (see Supporting Information).
-
tBuFeNPhNHPh. Many other control experiments were also performed to verify that the products do not react with each other or with byproducts (see Supporting Information).
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-
-
-
74
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34447123535
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We cannot rule out that the initiation step is N-N bond homolysis, which would give LtBuFeNPh (a potential chain carrier, as discussed below) and PhNH•, which would give a small amount of PhNH2 presumably undetected, After initiation, the chain would proceed as in Scheme 4
-
2 (presumably undetected). After initiation, the chain would proceed as in Scheme 4.
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75
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34447130548
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tBuFeNPhNHPh.
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Other recently isolated iron(III) species with a terminal imido ligand: (a) Brown, S. D.; Betley, T. A.; Peters, J. C. J. Am. Chem. Soc. 2003, 125, 322-323.
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II-NH(aryl) products, consistent with powerful H-atom abstraction ability of the putative imido. Eckert, N. A. Ph.D. Thesis, University of Rochester, 2005.
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Diketiminate-iron(I) complexes react with ketones to give pinacol coupling products: see ref 36. We have obtained ambiguous results when using other traps for iron(I) in the conversion of LtBuFeNPhNHPh to L tBuFeNHPh, as follows. PPh3 and PEt3 bind weakly to the LtBuFe fragment (see refs 36 and 41b) and do not affect the rate of conversion. CO does bind to LtBuFe (see ref 36, but does not affect the decomposition of LtBuFeNPhNHPh: this is consistent with the observation that addition of a small amount of L tBuFe(CO)2 to the LtBuFeNPhNHPh abolishes the induction period for its decomposition. Therefore, it is likely that CO binds reversibly to the LtBuFe fragment, and does not substantially affect the chain reaction
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tBuFe fragment, and does not substantially affect the chain reaction.
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Azobenzene loss may require an isomerization of the η2- bound ground state (Figure 6) to an η1 isomer, a process that can be slow: see ref 22o. We are unable to reconcile this rate-limiting step with the apparent negative value of ΔS‡ in footnote 27
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‡ in footnote 27.
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