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

Journal of the American Chemical Society
Sujan K SarkarAnna D Gudmundsdottir

Abstract

The photolysis of 2-azido-1,4-naphthoquinone (1) in argon matrices at 8 K results in the corresponding triplet vinylnitrene (3)2, which was detected directly by IR spectroscopy. Vinylnitrene (3)2 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 (3)2, which is stable up to at least 100 K. The zero-field splitting parameters for nitrene (3)2, D/hc = 0.7292 cm(-1) and E/hc = 0.0048 cm(-1), verify that it has significant 1,3-biradical character. Vinylnitrene (3)2 (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 (3)2 and the proposed mechanism for its formation. Because vinylnitrene (3)2 is relatively stable, it has potential use as a building-block for high-spin assemblies.

References

May 20, 2006·The Journal of Organic Chemistry·David KvaskoffCurt Wentrup
Nov 24, 2007·Journal of the American Chemical Society·Pradeep N D SinghAnna D Gudmundsdóttir
May 13, 2009·Organic Letters·Sivaramakrishnan MuthukrishnanAnna D Gudmundsdottir
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Dec 25, 2013·The Journal of Organic Chemistry·Xiaoming ZhangAnna D Gudmundsdottir
Aug 29, 2014·The Journal of Organic Chemistry·Sridhar RajamAnna D Gudmundsdottir

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Citations

Oct 25, 2016·Journal of the American Chemical Society·Sujan K SarkarAnna D Gudmundsdottir
May 29, 2018·Angewandte Chemie·Curt Wentrup
Feb 6, 2020·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Upasana BanerjeeAnna D Gudmundsdottir
Dec 11, 2020·Physical Chemistry Chemical Physics : PCCP·Jian LiZe-Sheng Li
Jul 28, 2019·Organic Letters·Dylan J ShieldsAnna D Gudmundsdottir
Jul 3, 2019·The Journal of Organic Chemistry·DeVonna M GatlinAnna D Gudmundsdottir
Feb 25, 2017·Chemical Reviews·Curt Wentrup
Sep 30, 2020·Journal of the American Chemical Society·Dylan J ShieldsPanče Naumov

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