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A modest kinetic isotope effect (KIE = 1.9; cyclohexane solvent) was observed in the photolysis of 2-azidobiphenyl by Sundberg and co-workers (ref 13d). They imply that this result suggests that the singlet nitrene does not insert directly into the ortho-C-H bond but rather adds to the carbon.
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Caution should be exercised in drawing firm conclusions from the nonlinearity of the Hammett correlation using σ values for electrophilic reactions. Refer to ref 29 for a detailed discussion.
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p values, the lines did not pass through the origin. See the Supporting Information or additional Hammett correlation plots.
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Smith and co-workers did not observe any linear correlation with Hammett substituent constants in the decomposition of 2-azidobiaryls. The reaction rate depended only on the arene bearing the azide group. See ref 11c.
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158
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69549119534
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The error in slope and intercept was determined using least-squares analysis.
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159
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69549097153
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When N-aryl-N-methylnitrenium ions were substituted with electron-donating groups, higher frequency aromatic C=C bond stretches were observed using time-resolved infared spectroscopy. Falvey and co-workers attributed the longer bond stretch to represent substantial charge delocalization in the aromatic system to favor a quinoid structure. See ref 17d.
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A 6π-electron-5-atom electrocyclization was posited as a potential mechanism in the related deoxygenation of nitroaromatics; see
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A related diradical mechanism was proposed for the isomerization of aryl-substituted azirines to indoles; see
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2-extrusion. We expect that the resulting nitrenoid to react faster with this ring than with the more electron-deficient ring, which is not necessarily in the plane.
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Some nucleophilic group 8 metal nitrenoid complexes have been reported. For leading examples, see: Ir
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