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

D Scott Bohle; Zhijie Chua; Inna Perepichka

doi:10.1002/cplu.201300245

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

Chempluschem. 2013 Oct;78(10):1304-1310. doi: 10.1002/cplu.201300245. Epub 2013 Jul 31.

Authors

D Scott Bohle¹, Zhijie Chua¹, Inna Perepichka¹

Affiliation

¹ Department of Chemistry, McGill University, 801 Sherbrooke St. W., Montreal, H3A 0B8 (Canada).

PMID: 31986781
DOI: 10.1002/cplu.201300245

Abstract

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 ¹⁹ F 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 [Ir^I (η¹ -NNPhNSO₂ C₄ F₉ )(Cl)(PPh₃ )₂ ] (2) or an unusual double bent diazene [Ir^III (η³ -NNPhNSO₂ Btz)(Cl)(PPh₃ )₂ ] (4; Btz=benzotriazole) complex.

Keywords: azo compounds; benzotriazoles; oxidative addition reactions; rearrangement; transition metals; vibrational spectroscopy.

Abstract

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