Direct Observation of an Imidoylnitrene: Photochemical Formation of PhC(=NMe)-N and Me-N from 1-Methyl-5-phenyltetrazole

Manabu Abe; Didier Bégué; Hugo Santos-Silva; Alain Dargelos; Curt Wentrup

doi:10.1002/anie.201712689

Direct Observation of an Imidoylnitrene: Photochemical Formation of PhC(=NMe)-N and Me-N from 1-Methyl-5-phenyltetrazole

Angew Chem Int Ed Engl. 2018 Mar 12;57(12):3212-3216. doi: 10.1002/anie.201712689. Epub 2018 Feb 21.

Authors

Manabu Abe¹, Didier Bégué², Hugo Santos-Silva², Alain Dargelos², Curt Wentrup³

Affiliations

¹ Department of Chemistry, Graduate School of Science, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, Hiroshima, 739-8526, Japan.
² Institut Pluridisciplinaire de Recherche sur l'Environnement et les Matériaux, Université de Pau et des Pays de l'Adour, 64000, Pau, France.
³ School of Chemistry and Molecular Biosciences, The University of Queensland, Brisbane, Queensland, 4072, Australia.

PMID: 29390171
DOI: 10.1002/anie.201712689

Abstract

The imidoylnitrene 8, N-methyl-C-phenylimidoylnitrene, has been generated by laser photolysis of 1-methyl-5-phenyltetrazole 6 at 5 K and characterized by its ESR spectrum (|D/hc|=0.9602, |E/hc|=0.0144 cm^-1 ). In addition, the triplet excited states of 6 and of 2-methyl-5-phenyltetrazole 11 were also observed by ESR spectroscopy in the 5 K matrices (6: |D/hc|=0.123 cm^-1 , E/hc=0.0065 cm^-1 , 11: |D/hc|=0.126 cm^-1 , |E/hc|=0.0056 cm^-1 ). The imidoylnitrene 8 is unstable both thermally (disappearing at 80 K) and photochemically (disappearing on continued irradiation at 266 nm). Methyl(phenyl)carbodiimide is the end product of photolysis.

Keywords: ESR spectroscopy; matrix isolation; nitrenes; tetrazoles; triplet excited states.

Publication types

Research Support, Non-U.S. Gov't