Facile NN Activation in Benzotriazole: Capturing the Dimroth Azo/Triazole Intermediate by Complexation to Iridium

The in situ observation of benzotriazole ring and ring‐opened isomers, which result from the Dimroth equilibrium for 1‐[(nonafluorobutane)sulfonyl]benzotriazole, 1, in solution by 19F NMR and UV/Vis spectroscopy is reported. Two benzotriazoles, compound 1 and 1,1′‐sulfonylbis(benzotriazole) (3), und...

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Bibliographic Details
Published in:ChemPlusChem (Weinheim, Germany) Germany), 2013-10, Vol.78 (10), p.1304-1310
Main Authors: Bohle, D. Scott, Chua, Zhijie, Perepichka, Inna
Format: Article
Language:English
Subjects:
azo compounds
benzotriazoles
oxidative addition reactions
rearrangement
transition metals
vibrational spectroscopy
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Summary:The in situ observation of benzotriazole ring and ring‐opened isomers, which result from the Dimroth equilibrium for 1‐[(nonafluorobutane)sulfonyl]benzotriazole, 1, in solution by 19F NMR and UV/Vis spectroscopy is reported. Two benzotriazoles, compound 1 and 1,1′‐sulfonylbis(benzotriazole) (3), undergo Dimroth triazole ring opening and coordination to an iridium(I) metal center to give either linear diazo [IrI(η1‐NNPhNSO2C4F9)(Cl)(PPh3)2] (2) or an unusual double bent diazene [IrIII(η3‐NNPhNSO2Btz)(Cl)(PPh3)2] (4; Btz=benzotriazole) complex. The obdurate benzotriazole ring: The in situ observation of benzotriazole ring and ring‐opened isomers, which result from the Dimroth equilibrium for 1‐[(nonafluorobutane)sulfonyl]benzotriazole in solution by 19F NMR and UV/Vis spectroscopy is reported (see scheme). Low‐valent organometallic complexes offer the possibility of trapping the azo isomer and potentially promoting NN activation and ring opening of benzotriazoles.
ISSN:2192-6506
2192-6506
DOI:10.1002/cplu.201300245