CFNO‐Isomere — Theoretische und experimentelle Studien

Jacobs, J.; Jülicher, Bernd; Schatte, Gabriele; Willner, Helge; Mack, Hans‐Georg

doi:10.1002/cber.19931261003

Cited by 21 publications

(30 citation statements)

References 24 publications

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“…For comparison, the vibrational spectra of various FCNO isomers were calculated at different levels of theory (Table S1 in the Supporting Information). The band positions and relative intensities of the newly formed species (labeled b in Figure 1) can unambiguously be attributed to triplet FC(O)N by comparison with its predicted IR spectrum also shown in Figure 1 The vibrational mode assignments given in Table 1 With the experimental IR spectrum of FC(O)N in hand we were able to attribute some of the previously reported [10] unassigned bands to triplet nitrene, and eventually, after some reassignments, the full sets of 12/13 C and 16/18 O isotopic shift data were accessible from the previously measured spectra. [10] The fundamental band positions of FC(O)N and their relative intensities and isotopic shifts reveal a strikingly good agreement with data predicted at the B3LYP/6-311 + GA C H T U N G T R E N N U N G (3df) level of theory (Table 1 and Figure 1).…”

Section: Wwwchemeurjorgmentioning

confidence: 87%

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The Missing Link: Triplet Fluorocarbonyl Nitrene FC(O)N

Zeng

Beckers

Willner

et al. 2011

Chemistry A European J

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The elusive triplet fluorocarbonyl nitrene, FC(O)N (X(3 A''), has been generated in high yield from matrix-isolated FC(O)N(3) by ArF excimer laser photolysis (λ=193 nm). As a side product FNCO was formed. The novel nitrene was characterized by IR, UV/Vis, EPR spectroscopy, and quantum-chemical calculations. All six fundamental vibrations of FC(O)N at 1681.3, 1193.8, 879.8, 646.5, 588.7, and 434.8 cm(-1) (argon matrix, 16 K), their (12/13)C, (16/18)O, and (14/15)N isotopic shifts, and four electronic transitions at T(0) =13 890, 25 428, 29 166, and 30 900 cm(-1) that exhibit vibrational fine structures have been detected. Under visible-light irradiation at λ≥495 nm, FC(O)N reacted with molecular N(2) in the matrix cage at 6 K to give back FC(O)N(3), whereas near-UV irradiation at λ≥335 nm yielded FNCO. The singlet-triplet energy gaps of different carbonyl nitrenes are discussed.

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Section: Wwwchemeurjorgmentioning

confidence: 87%

“…[10] In these experiments the formation of FNCO and various secondary photolysis products were reported. [10] Although the intervention of the nitrene FC(O)N during the photolysis of FC(O)N 3 was proved by its efficient interception with CO as FC(O)NCO, it could not be assigned conclusively in the IR spectra of the photolysis products.…”

Section: Introductionmentioning

confidence: 97%

The Missing Link: Triplet Fluorocarbonyl Nitrene FC(O)N

Zeng

Beckers

Willner

et al. 2011

Chemistry A European J

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“…[15] For instance, the ArF laser photolysis of the matrix-isolateda cyl azide FC(O)N 3 enabled the direct observation of the carbonyl nitrene FC(O)N, [15a] which was not observed in ap revious study of the photolysis in solid matricesb yu sing am ercuryl amp (l > 200 nm). [16] The use of the short-pulseArF laser has the distinct advantage of reducing secondary irradiation of the photolabile a-oxonitrenes by the unwanted UV or visible light from the mercury or xenon lamps.…”

Section: Introductionmentioning

confidence: 99%

Direct Observation of Carbamoylnitrenes

Wan

et al. 2016

Chemistry A European J

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As the prototype Curtius rearrangement reaction, carbamoyl azide decomposes into aminoisocyanate and molecular nitrogen. However, the key intermediate carbamoylnitrene was previously undetected, even though the decomposition of carbamoyl azides has been studied frequently since its discovery in the 1890s. Upon ArF laser (λ=193 nm) photolysis, the stepwise decomposition of the two simplest carbamoyl azides H2 NC(O)N3 and Me2 NC(O)N3, isolated in solid noble gas matrices, occurs with the formation of the corresponding carbamoylnitrenes H2 NC(O)N and Me2 NC(O)N. Both triplet species are characterized for the first time by combining matrix-isolation IR spectroscopy and quantum-chemical calculations. Subsequent visible-light irradiations cause efficient rearrangement of these nitrenes into the respective aminoisocyanates.

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“…Fluorocarbonyl azide, FC(O)N 3 , was prepared according to a reported procedure [24] with minor modifications concerning the reaction vessel. Instead of small flame-sealed ampules, tube-like glass vessels were used (volume 25 mL, length 20 cm), which were equipped with a valve fitted with a PTFE stem (Young, London, UK).…”

Section: Methodsmentioning

confidence: 99%

Fascinating Diazirinone: A Violet Gas

et al. 2012

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Keywords: Small ring systems / Matrix isolation / IR spectroscopy / Raman spectroscopy / UV/Vis spectroscopy / Electronic structure / Ab initio calculations Diazirinone (cyclic N 2 CO) recently identified in solid noble gas matrices and in the gas phase by infrared spectroscopy, has now been trapped at -196°C as a neat brownish-yellow solid, and characterized by low-temperature IR and Raman spectroscopy. Evaporation of the solid yields violet gaseous N 2 CO, which is surprisingly stable in a clean quartz cell. Its decay at room temperature in the dark follows a second-order rate law (k 2 = 4.9ϫ 10 -2 L mol -1 s -1 ) with a half-life of 30 h at an initial pressure of 5 mbar. The visible absorption spec-[a]

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CFNO‐Isomere — Theoretische und experimentelle Studien

Cited by 21 publications

References 24 publications

The Missing Link: Triplet Fluorocarbonyl Nitrene FC(O)N

The Missing Link: Triplet Fluorocarbonyl Nitrene FC(O)N

Direct Observation of Carbamoylnitrenes

Fascinating Diazirinone: A Violet Gas

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