Direct detection of a triplet vinylnitrene, 1,4-naphthoquinone-2-ylnitrene, in solution and cryogenic matrices

Sarkar, Sujan K, Sawai, Asako, Kanahara, Kousei, Wentrup, Curt, Abe, Manabu and Gudmundsdottir, Anna D (2015) Direct detection of a triplet vinylnitrene, 1,4-naphthoquinone-2-ylnitrene, in solution and cryogenic matrices. Journal of the American Chemical Society, 137 12: 4207-4214. doi:10.1021/jacs.5b00998


Author Sarkar, Sujan K
Sawai, Asako
Kanahara, Kousei
Wentrup, Curt
Abe, Manabu
Gudmundsdottir, Anna D
Title Direct detection of a triplet vinylnitrene, 1,4-naphthoquinone-2-ylnitrene, in solution and cryogenic matrices
Journal name Journal of the American Chemical Society   Check publisher's open access policy
ISSN 1520-5126
0002-7863
Publication date 2015-04-01
Sub-type Article (original research)
DOI 10.1021/jacs.5b00998
Volume 137
Issue 12
Start page 4207
End page 4214
Total pages 8
Place of publication Washington, United States
Publisher American Chemical Society
Collection year 2016
Language eng
Formatted abstract
The photolysis of 2-azido-1,4-naphthoquinone (1) in argon matrices at 8 K results in the corresponding triplet vinylnitrene 32, which was detected directly by IR spectroscopy. Vinylnitrene 32, is stable in argon matrices but forms 2-cyanoindane-1,3-dione (3) upon further irradiation. Similarly, the irradiation of azide 1 in 2-methyltetrahydrofuran (MTHF) matrices at 5 K resulted in the ESR spectrum of vinylnitrene 32, which is stable up to at least 100 K. The zero-field splitting parameters for nitrene 32, D/hc = 0.7292 cm–1 and E/hc = 0.0048 cm–1, verify that it has significant 1,3-biradical character. Vinylnitrene 32 (λmax ∼ 460 nm, τ = 22 μs) is also observed directly in solution at ambient temperature with laser flash photolysis of 1. Density functional theory (DFT) calculations support the characterization of vinylnitrene 32 and the proposed mechanism for its formation. Because vinylnitrene 32 is relatively stable, it has potential use as a building-block for high-spin assemblies.
Q-Index Code C1
Q-Index Status Confirmed Code
Institutional Status UQ

Document type: Journal Article
Sub-type: Article (original research)
Collections: Official 2016 Collection
School of Chemistry and Molecular Biosciences
 
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