Low-temperature matrix isolation of the 1,1-diazene H2NN. Electronic and infrared characterization

Sylwester, Alan P.; Dervan, Peter B.

doi:10.1021/ja00328a076

Cited by 44 publications

(21 citation statements)

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“…By referring to the previously reported IR spectrum of H 2 NNCO in solid Ar, its production after the laser photolysis can be ascertained by the characteristic IR bands at

\overset{ν}{true}

=2263.7 and 2215.7 cm −1 (denoted with “c” in Figure A) for the antisymmetric NCO stretching vibration. Traces of CO (

\overset{ν}{true}

=2144.6 cm −1 in Ne matrix) were also formed, whereas the IR bands of the remaining fragment H 2 NN could not be clearly identified due to overlap with the strong IR bands of the azide precursor (denoted with “a” in Figure A).…”

Section: Resultsmentioning

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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“…By referring to the previously reported IR spectrum of H 2 NNCO in solid Ar, its production after the laser photolysis can be ascertained by the characteristic IR bands at

\overset{ν}{true}

=2263.7 and 2215.7 cm −1 (denoted with “c” in Figure A) for the antisymmetric NCO stretching vibration. Traces of CO (

\overset{ν}{true}

Section: Resultsmentioning

confidence: 99%

Direct Observation of Carbamoylnitrenes

Wan

et al. 2016

Chemistry A European J

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“…There have been several theoretical [1][2][3][4][5][6][7][8][9][10][11][12][13] and experimental [14][15][16][17][18][19] studies of the title system (a more complete list of earlier theoretical and experimental work is given in Refs. [3,2]).…”

Section: Introductionmentioning

confidence: 99%

“…[3,2]). Some of these studies focused on the determination of accurate geometries, frequencies and relative stabilities of three local minima: trans-, cis-, and iso-N 2 H 2 [3,7,[14][15][16][17][18][19]11,10]. Moreover, there has been considerable theoretical work [2,1,9,4,8,6,5,12,13] on the determination of the barriers involved in the diimide isomerization or formation processes, often for testing the accuracy of theoretical methods that are used to study chemical reactions [13,12,4,6].…”

Section: Introductionmentioning

confidence: 99%

Accurate MRCI study of ground-state N2H2 potential energy surface

Biczysko

Poveda

Varandas

2006

Chemical Physics Letters

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Extensive ab initio calculations have been performed to determine the energy, geometry and vibrational frequencies of all stationary points of the N 2 H 2 ground-state potential energy surface. The geometries of trans-, cis-and iso-minima as well as transition states are reported at the MCSCF/aug-cc-pVQZ level, while the relative energetics is established by single point MRCI/aug-cc-pVQZ calculations including the Davidson size-consistency correction. The data is useful for modeling a single-sheeted global potential energy surface for the title system.

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“…Derwan (SD) [19]. Teles et al (TMHS) [20] obtained isodiazene by photolysis of aminoisocyanates in argon at 12 K, and recorded a complete infrared spectrum which they assigned with the help of fairly low-level ab initio harmonic frequency calculations.…”

Section: Introductionmentioning

confidence: 99%

Benchmark ab initio thermochemistry of the isomers of diimide, N2H2, using accurate computed structures and anharmonic force fields

Martin

1999

Molecular Physics

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A benchmark ab initio study on the thermochemistry of the trans-HNNH, cis-HNNH, and H 2 NN isomers of diazene has been carried out using the CCSD(T) coupled cluster method, basis sets as large as [7s6p5d4f 3g2h/5s4p3d2f 1g], and extrapolations towards the 1-particle basis set limit. The effects on innershell correlation and of anharmonicity in the zero-point energy were taken into account: accurate geometries and anharmonic force fields were thus obtained as by-products. Our best computed ∆H

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Low-temperature matrix isolation of the 1,1-diazene H2NN. Electronic and infrared characterization

Cited by 44 publications

References 0 publications

Direct Observation of Carbamoylnitrenes

Direct Observation of Carbamoylnitrenes

Accurate MRCI study of ground-state N2H2 potential energy surface

Benchmark ab initio thermochemistry of the isomers of diimide, N2H2, using accurate computed structures and anharmonic force fields

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