Transforming Triplet Vinylnitrene into Triplet Alkylnitrene at Cryogenic Temperatures

Photolysis of 2,3-diazidonaphthalene-1,4-dione (1) in methyltetrahydrofuran matrices forms 2-(λ1-azaneyl)-3-azidonaphthalene-1,4-dione (vinylnitrene 3 2), as confirmed by electron paramagnetic resonance spectroscopy. The zero-field splitting (zfs) parameters for 3 2 (D/hc = 0.5338 cm–1, and E/hc = 0...

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Published inOrganic letters Vol. 21; no. 18; pp. 7194 - 7198
Main Authors Shields, Dylan J, Sarkar, Sujan K, Sriyarathne, H. Dushanee M, Brown, Jocelyn R, Wentrup, Curt, Abe, Manabu, Gudmundsdottir, Anna D
Format Journal Article
LanguageEnglish
Published United States American Chemical Society 20.09.2019
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Summary:Photolysis of 2,3-diazidonaphthalene-1,4-dione (1) in methyltetrahydrofuran matrices forms 2-(λ1-azaneyl)-3-azidonaphthalene-1,4-dione (vinylnitrene 3 2), as confirmed by electron paramagnetic resonance spectroscopy. The zero-field splitting (zfs) parameters for 3 2 (D/hc = 0.5338 cm–1, and E/hc = 0.0038 cm–1) reveal significant 1,3-biradical character. Irradiating 3 2 yields 2-(λ1-azaneyl)-1,3-dioxo-2,3-dihydro-1H-indene-2-carbonitrile (alkylnitrene 3 3), which has zfs parameters typical of a cycloalkylnitrene (D/hc = 1.57 cm–1, and E/hc = 0.00071 cm–1). Photolysis of 1 in argon matrices verifies that 3 2 forms 3 3.
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ISSN:1523-7060
1523-7052
DOI:10.1021/acs.orglett.9b01950